Method for producing fibrous product

Abstract

To provide a method for producing a fibrous product demonstrating excellent water repellency.SOLUTION: This method for producing a fibrous product includes: bringing an isocyanate compound into contact with a fibrous material; and bringing a non-fluorine-based water-repellent component into contact with the fibrous material that has already been brought into contact with the isocyanate compound.SELECTED DRAWING: None

Description

Technical Field

[0001] This application discloses a method for manufacturing textile products.

Background Art

[0002] Fluorine-based water repellents having fluorine-containing groups are known. By treating articles such as textile products with a fluorine-based water repellent, excellent water repellency can be imparted to the articles. Fluorine-based water repellents are generally produced by polymerizing or copolymerizing monomers having fluoroalkyl groups. In order to exhibit sufficient water repellency, it is necessary to align the fluoroalkyl groups. Usually, after attaching a fluorine-based water repellent to an article, heat treatment is performed at a temperature exceeding 130°C. However, performing such heat treatment is not desirable from the viewpoint of energy saving. In addition, monomers having fluoroalkyl groups are not only expensive but also hardly decomposable, so they have a large environmental load. For these reasons, in recent years, techniques for imparting excellent water repellency to articles such as textile products by treating them with non-fluorine-based water repellents that do not contain fluorine have been studied. For example, Patent Documents 1 to 3 disclose techniques for bringing a non-fluorine-based water repellent into contact with fibers pretreated with an anionic compound.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the prior art using non-fluorine-based water repellents, there is still room for improvement. For example, the washing durability water repellency in natural fibers and the water repellency under severe conditions such as the Bundesmann rainfall test in synthetic fibers may not be sufficient. In this regard, a new technology capable of imparting excellent water repellency to fiber products (for example, washing durability water repellency in natural fibers and water repellency after the Bundesmann rainfall test (Bundesmann water repellency) in synthetic fibers) is required.

Means for Solving the Problems

[0005] As means for solving the above problems, the present application discloses the following multiple aspects. <Aspect 1> Bringing an isocyanate compound into contact with a fiber material, and Bringing a non-fluorine-based water repellent component into contact with the fiber material after bringing it into contact with the isocyanate compound, A method for manufacturing a fiber product, comprising: <Aspect 2> The isocyanate compound is a polyisocyanate, The method for manufacturing a fiber product according to Aspect 1. <Aspect 3> The isocyanate compound is at least one of an aliphatic isocyanate, an aromatic isocyanate, an aromatic aliphatic isocyanate, and an alicyclic isocyanate, The method for manufacturing a fiber product according to Aspect 1 or 2. <Aspect 4> The isocyanate compound is an unblocked isocyanate, The method for manufacturing a fiber product according to any one of Aspects 1 to 3. <Aspect 5> The non-fluorine-based water repellent component is at least one of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound, The method for manufacturing a fiber product according to any one of Aspects 1 to 4.

Advantages of the Invention

[0006] According to the manufacturing method of the present disclosure, after bringing an isocyanate compound into contact with a fiber material, a non-fluorine-based water-repellent component is brought into contact therewith, so that the adhesiveness of the non-fluorine-based water-repellent component to the fiber material is improved, and excellent water repellency can be imparted to the fiber material. According to the technology of the present disclosure, for example, a fiber product having excellent initial water repellency, durable water repellency, and Bundesmann water repellency can be manufactured.

Brief Description of the Drawings

[0007]

Figure 1

Embodiments for Carrying Out the Invention

[0008] Hereinafter, a method for manufacturing a fiber product according to an embodiment will be described, but the method for manufacturing a fiber product of the present disclosure is not limited to this embodiment.

[0009] A method for manufacturing a fiber product according to an embodiment includes bringing an isocyanate compound into contact with a fiber material, and bringing a non-fluorine-based water-repellent component into contact with the fiber after bringing it into contact with the isocyanate compound. In other words, a method for manufacturing a fiber product according to an embodiment performs a water-repellent treatment with a non-fluorine-based water-repellent component after performing a pretreatment on the fiber material with an isocyanate compound.

[0010] 1. Pretreatment In a method for manufacturing a fiber product according to an embodiment, as a pretreatment, an isocyanate compound is brought into contact with a fiber material.

[0011] 1.1 Fiber Material There are no particular restrictions on the type of fiber material. The fiber material may be at least one selected from natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including cross-knitting), woven fabric (including cross-weaving), non-woven fabric, and paper. In the water-repellent fiber product according to one embodiment, from the viewpoint of having better water repellency, the fiber material preferably contains polyamide and polyester as raw materials. In particular, it is preferably at least one selected from nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0012] 1.2 Pretreatment agent In the method for manufacturing a fiber product according to one embodiment, an isocyanate compound is brought into contact with the above fiber material. For example, a pretreatment agent containing an isocyanate compound is prepared, and the pretreatment agent is brought into contact with the fiber material. The pretreatment agent contains an isocyanate compound and may further optionally contain components other than the isocyanate compound (other components).

[0013] 1.2.1 Isocyanate compound The isocyanate compound is a compound having an isocyanate group, and any compound that can adhere to the fiber may be used. For example, the isocyanate compound may be a polyisocyanate. Further, the isocyanate compound may be at least one of an aliphatic isocyanate, an aromatic isocyanate, an aromatic aliphatic isocyanate, and an alicyclic isocyanate. Further, the isocyanate compound may be a blocked isocyanate or an unblocked isocyanate. In particular, when the isocyanate compound is an unblocked isocyanate, a more excellent water repellent effect can be expected. The isocyanate compound can be used alone or in combination of two or more. Further, the isocyanate compound may be a reaction product of two or more isocyanate compounds.

[0014] (Polyisocyanate) The isocyanate compound may be a polyisocyanate. Examples of the polyisocyanate include a polyisocyanate monomer and a polyisocyanate derivative. The polyisocyanate means an isocyanate compound having a plurality of isocyanate groups in the same compound molecule. Similarly, the diisocyanate compound means an isocyanate compound having two isocyanate groups in the same compound molecule. These polyisocyanates can be used alone or in combination of two or more.

[0015] There is no particular limitation on the polyisocyanate monomer, and examples thereof include an aliphatic polyisocyanate, an aromatic polyisocyanate, an aromatic aliphatic polyisocyanate, and an alicyclic polyisocyanate. These polyisocyanate monomers can be used alone or in combination of two or more.

[0016] The polyisocyanate derivative is not particularly limited. For example, multimers of polyisocyanate monomers (e.g., dimers, trimers (e.g., isocyanurate-modified products, iminooxadiazinedione-modified products), pentamers, heptamers, etc.), allophanate-modified products (e.g., allophanate-modified products formed by further addition of the isocyanate group of a polyisocyanate monomer to the urethane group formed by the reaction of the above-mentioned polyisocyanate monomer and a low-molecular-weight polyol described later, etc.), adduct products (e.g., adduct products (alcohol adducts) formed by the reaction of a polyisocyanate monomer and a low-molecular-weight polyol described later, etc.), biuret-modified products (e.g., biuret-modified products formed by the reaction of the above-mentioned polyisocyanate monomer with water or amines, etc.), urea-modified products (e.g., urea-modified products formed by further addition of the isocyanate group of a polyisocyanate monomer to the urea group formed by the reaction of the above-mentioned polyisocyanate monomer and a diamine, etc.), oxadiazinetrione-modified products (e.g., oxadiazinetrione formed by the reaction of the above-mentioned polyisocyanate monomer with carbon dioxide gas, etc.), carbodiimide-modified products (e.g., carbodiimide-modified products formed by the decarboxylation condensation reaction of the above-mentioned polyisocyanate monomer, etc.), uretdione-modified products, uretonimine-modified products, etc. can be mentioned. Further, as the polyisocyanate derivative, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI), etc. can also be mentioned. These polyisocyanate derivatives can be used alone or in combination of two or more.

[0017] From the viewpoint of the water repellency of the bondisman, the polyisocyanate is preferably a multimer of the above monomer. In particular, when the polyisocyanate is a trimer, the water repellency of the bondisman is more likely to be improved.

[0018] As described above, the polyisocyanate may be used alone as one kind or in combination of two or more kinds. Further, the polyisocyanate may be a reaction product of two or more kinds of isocyanate compounds. When two or more kinds of polyisocyanates are used in combination, a combination of an aliphatic and an alicyclic polyisocyanate is preferable. In this case, the mass ratio of the aliphatic polyisocyanate to the alicyclic polyisocyanate is preferably from 99 / 1 to 1 / 99, more preferably from 90 / 10 to 10 / 90, still more preferably from 80 / 20 to 20 / 80, and most preferably from 75 / 25 to 50 / 50. When the aliphatic polyisocyanate and the alicyclic polyisocyanate are contained in this ratio, the durability water repellency of the binder is further improved.

[0019] (Aliphatic isocyanate) The aliphatic isocyanate may be at least one selected from, for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, lysine diisocyanate, dimer acid diisocyanate, etc. From the viewpoint of excellent washing durability water repellency in natural fibers, 1,6-hexamethylene diisocyanate (HDI) is preferable.

[0020] (Aromatic isocyanate) The aromatic isocyanate may be at least one selected from, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, and the like.

[0021] (Aromatic aliphatic isocyanate) The aromatic aliphatic isocyanate may be at least one selected from, for example, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, and the like.

[0022] (Alicyclic isocyanate) Aliphatic isocyanates may be at least one selected from, for example, 1,3 - cyclopentane diisocyanate, 1,3 - cyclopentene diisocyanate, cyclohexane diisocyanate (1,4 - cyclohexane diisocyanate, 1,3 - cyclohexane diisocyanate), 3 - isocyanatomethyl - 3,5,5 - trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylene bis(cyclohexyl isocyanate) (4,4’ -, 2,4’ - or 2,2’ - methylene bis(cyclohexyl isocyanate), their Trans,Trans - form, Trans,Cis - form, Cis,Cis - form, or a mixture thereof) (H12MDI, hydrogenated MDI), methylcyclohexane diisocyanate (methyl - 2,4 - cyclohexane diisocyanate, methyl - 2,6 - cyclohexane diisocyanate), norbornane diisocyanate (various isomers or a mixture thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3 - or 1,4 - bis(isocyanatomethyl)cyclohexane or a mixture thereof) (H6XDI, hydrogenated XDI), etc. From the viewpoint of excellent Bondesmann durable water repellency, the aliphatic isocyanate is preferably at least one of isophorone diisocyanate (IPDI), hydrogenated MDI, and hydrogenated XDI, more preferably at least one of isophorone diisocyanate (IPDI) and hydrogenated MDI, and still more preferably isophorone diisocyanate (IPDI).

[0023] (Blocked Isocyanate / Unblocked Isocyanate) The isocyanate compound may or may not be blocked by a blocking agent. In particular, from the viewpoint of durable water repellency, the isocyanate compound is preferably an unblocked isocyanate (unblocked isocyanate). The blocked isocyanate can be obtained by reacting the above - mentioned isocyanate compound with a blocking agent. The blocking agent may be used alone as one kind or in combination of two or more kinds.

[0024] The blocking agent may be, for example, a compound having one or more active hydrogens in the molecule. The blocking agent may be, for example, at least one selected from alcohol-based compounds, alkylphenol-based compounds, phenol-based compounds, active methylene-based compounds, mercaptan-based compounds, acid amide-based compounds, acid imide-based compounds, imidazole-based compounds, imidazoline-based compounds, triazole-based compounds, carbamic acid-based compounds, urea-based compounds, oxime-based compounds, amine-based compounds, imide-based compounds, imine-based compounds, pyrazole-based compounds, and bisulfites. Among them, at least one selected from acid amide-based compounds, active methylene-based compounds, oxime-based compounds, and pyrazole-based compounds is preferable. For example, at least one selected from ε-caprolactam, acetylacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, and 3,5-dimethylpyrazole is preferable. Among them, from the viewpoint of washing durability and water repellency, one or both of dimethylpyrazole and malonic acid diester are more preferable.

[0025] (Self-emulsifying property) The above isocyanate compound may or may not have self-emulsifying properties. Examples of isocyanate compounds having self-emulsifying properties include those in which a nonionic hydrophilic group, a cationic hydrophilic group, or an anionic hydrophilic group is introduced into a part of the polyisocyanate. From the viewpoint of water repellency, a polyisocyanate having a nonionic hydrophilic group having an oxyethylene group introduced therein can preferably be used. Examples of hydrophilic compounds reacted with the polyisocyanate to impart self-emulsifying properties include polyoxyalkylene monoalkyl ethers such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol polypropylene glycol monomethyl ether, and polypropylene glycol polyethylene glycol monobutyl ether; (poly)ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol; block copolymers, random copolymers of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and random copolymers and block copolymers of ethylene oxide and propylene oxide, and ethylene oxide and butylene oxide; polyoxyalkylene monoamines, polyoxyalkylene diamines; and the like. Polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, etc. are preferably used. The above nonionic hydrophilic compounds may be used alone or in combination of two or more. By introducing these compounds in an amount of about 1 to 50 mol% based on the isocyanate group, self-emulsifying properties can be imparted to the isocyanate compound.

[0026] 1.2.2 Other Components The pretreatment agent may contain other components such as a solvent and an emulsifier, in addition to the above isocyanate compound, for example.

[0027] (Solvent) The pretreatment agent may contain, for example, water, an organic solvent, or a mixture of water and an organic solvent. Examples of the organic solvent include ether solvents, ketone solvents, hydrocarbon solvents, aromatic solvents, ester solvents, nitrogen-containing solvents, and the like. The amount of the solvent may be 0.1 to 70% by mass, 5 to 50% by mass, or 10 to 30% by mass, with the total amount of the pretreatment agent being 100% by mass.

[0028] (Emulsifier) The pretreatment agent may contain an emulsifier to improve the dispersibility of an isocyanate compound or the like in the above solvent. The emulsifier may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In the case of blocked isocyanate, from the viewpoint of water repellency, it is preferably a nonionic surfactant alone or a combination of a nonionic surfactant and a cationic surfactant. In the combination of a nonionic surfactant and a cationic surfactant, the mass ratio of the nonionic surfactant to the cationic surfactant may be, for example, 99.5:0.5 to 50:50, or 99:1 to 90:10. In the case of unblocked isocyanate, an anionic surfactant is most preferred from the viewpoint of protecting the isocyanate group.

[0029] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, fatty acid alkanolamides, alkyl alkanolamides, acetylene glycols, oxyethylene adducts of acetylene glycols, polyethylene glycol polypropylene glycol block copolymers, and the like. Examples of anionic surfactants include sulfate salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkyl phenyl ether phosphates, and the like. Examples of cationic surfactants include amine salts, amide amine salts, quaternary ammonium salts, and imidazolinium salts. Specific examples include, but are not particularly limited to, amine salt-type surfactants such as alkylamine salts, polyoxyethylene alkylamine salts, alkylamide amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, and benzethonium chloride. Examples of amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amide betaines, betaine acetates, and the like. Specifically, long-chain amine oxides, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetate betaine, fatty acid amide propyl dimethylaminoacetate betaine, and the like can be mentioned.The amount of these surfactants used is not particularly limited. For example, among the solid content of the emulsion, 1 to 20% by mass is preferable, and more preferably 1.5 to 10% by mass.

[0030] The hydrophilic-lipophilic balance (HLB) of the above emulsifier is not particularly limited. In one embodiment, the average HLB of the nonionic emulsifier in the pretreatment agent is preferably 6.0 to 16.0, 6.5 to 15.5, 7.0 to 15.0, or 7.5 to 14.5. When the HLB is outside this range, the initial Bundesmann water repellency and the Bundesmann water repellency after wear tend to decrease. The HLB of the emulsifier is defined as the value obtained from the following formula by the Griffin method, considering the ethyleneoxy group in the surfactant as the hydrophilic group. HLB = 20 × [(molecular weight of hydrophilic group contained in surfactant) / (molecular weight of surfactant)]

[0031] (Other additives) The pretreatment agent may contain an acid, an alkali, a chelating agent, etc.

[0032] 1.2.3 Content of isocyanate compound The content of the isocyanate compound in the pretreatment agent is not particularly limited. For example, the ratio (mass ratio) of the isocyanate compound in the whole pretreatment agent may be 0.01 to 80%, or 0.1 to 70%.

[0033] 1.3 Contact method In the method for manufacturing a fiber product according to an embodiment, the isocyanate compound (a pretreatment agent containing the isocyanate compound) can be adhered to the fiber material by bringing the above-described isocyanate compound into contact with the above-described fiber material. The method of bringing the above-described isocyanate compound (a pretreatment agent containing the isocyanate compound) into contact with the above-described fiber material is not particularly limited. For example, processing methods such as an immersion method, a spraying method, and a coating method can be mentioned. The immersion method may be a continuous method or a batch method. In the continuous method, first, the isocyanate compound is diluted in a solvent to prepare a pretreatment agent (treatment liquid). Next, the object to be treated (fiber material) is continuously fed into an impregnation device filled with the treatment liquid, the object to be treated is impregnated with the treatment liquid, and then unnecessary treatment liquid is removed. The impregnation device is not particularly limited, and a padder, a kiss roll type application device, a gravure coater type application device, a spray type application device, a foam type application device, a coating type application device, etc. can be preferably adopted, and a padder type is particularly preferable. Subsequently, an operation of removing the solvent remaining on the object to be treated using a dryer is performed. The dryer is not particularly limited, and a spread dryer such as a hot flue or a tenter is preferable. The continuous method is preferably adopted when the object to be treated is in the form of a fabric such as a woven fabric. On the other hand, the batch method includes, for example, a step of immersing the object to be treated in the treatment liquid and a step of removing the solvent remaining on the treated object. The batch method is preferably adopted when the object to be treated is not in the form of a fabric, for example, in the case of loose wool, top, sliver, roving, tow, yarn, etc., or when it is not suitable for the continuous method such as a knitted fabric. In the immersion step, for example, a vat dyeing machine, a cheese dyeing machine, a jet dyeing machine, an industrial washing machine, a beam dyeing machine, etc. can be used. In the operation of removing the solvent, a hot air dryer such as a cheese dryer, a beam dryer, a tumble dryer, a high-frequency dryer, etc. can be used.

[0034] 1.4 Drying It is preferable that the fibrous material be sufficiently dried after being brought into contact with a pretreatment agent (treatment liquid). As the temperature of the dry heat treatment, 100 to 200°C is preferable, and particularly 120 to 180°C is preferable. As the time of the dry heat treatment, 10 seconds to 3 minutes is preferable, and particularly 1 to 2 minutes is preferable. The method of the dry heat treatment is not particularly limited, but when the object to be treated is in the form of a fabric, a tenter is preferable.

[0035] 1.5 Adhesion amount An isocyanate compound adheres to the fibrous material after the pretreatment. The treatment with the pretreatment agent is preferably carried out in such an amount that the adhesion amount of the isocyanate compound is 0.01 to 3 parts by mass, or 0.1 to 1 part by mass with respect to 100 parts by mass of the fibrous material. Within this range, high-level durability water repellency and texture can be achieved simultaneously.

[0036] 2. Water repellent treatment In the method for producing a fiber product according to one embodiment, a non-fluorine-based water repellent component is brought into contact with the fibrous material after the above pretreatment (after being brought into contact with the isocyanate compound). For example, a water repellent treatment agent containing a non-fluorine-based water repellent component is prepared, and the water repellent treatment agent is brought into contact with the fibrous material.

[0037] 2.1 Water repellent treatment agent The water repellent treatment agent contains a non-fluorine-based water repellent component, and may further optionally contain components other than the non-fluorine-based water repellent component (other components).

[0038] 2.1.1 Non-fluorine-based water repellent component The non-fluorine-based water repellent component may be, for example, at least one of an acrylic-based compound, a silicone-based compound, a wax-based compound, and a dendrimer-based compound. From the viewpoints of durable water repellency and Bundesmann water repellency, one or both of an acrylic-based compound and a silicone-based compound are preferable, and a silicone-based compound is more preferable.

[0039] (Acrylic-based compound) The acrylic compound has a structural unit derived from, for example, a (meth)acrylic acid ester monomer represented by the following general formula (A1) (hereinafter also referred to as the “component (A1)”). The acrylic compound may further have a structural unit derived from a compound represented by the following general formula (A2) (hereinafter also referred to as the “component (A2)”). In the present application, “(meth)acrylic acid ester” means “acrylic acid ester” or the corresponding “methacrylic acid ester”, and the same applies to “(meth)acrylic acid”, “(meth)acrylamide”, etc.

[0040] [Chemical formula] [In formula (A1), R 1 is hydrogen or a methyl group, and R 2 is a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent.]

[0041] [Chemical formula] [In formula (A2), R 11 is hydrogen or a methyl group, R 12 is a divalent hydrocarbon group having 1 to 6 carbon atoms, Z is an ester group or an amide group, and W is a group represented by -CO-R 13 (R 13 is a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH 2 , or a group represented by the following formula (W1).

[0042] [Chemical formula]

[0043] The above component (A1) has a monovalent hydrocarbon group with 12 to 30 carbon atoms which may have a substituent. This hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic or aromatic cyclic structure. Among these, from the viewpoint of water repellency, those that are linear are preferred, and those that are linear alkyl groups are more preferred. In this case, the water repellency will be more excellent. When the monovalent hydrocarbon group with 12 to 30 carbon atoms has a substituent, examples of the substituent include one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. In the above general formula (A-1), R 2 is preferably an unsubstituted hydrocarbon group.

[0044] The carbon number of the above hydrocarbon group is preferably 12 to 24, and more preferably 12 to 22. When the carbon number is within this range, the water repellency and texture will be particularly excellent. Particularly preferred as the hydrocarbon group is a linear alkyl group having 18 to 22 carbon atoms.

[0045] Examples of the above component (A1) include at least one selected from stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, and behenyl (meth)acrylate.

[0046] The above component (A1) can have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent. In this case, the durable water repellency can be further improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Also, when the above component (A1) has an amino group, the texture can be further improved.

[0047] The above component (A1) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

[0048] The above component (A1) may be used alone or in combination of two or more.

[0049] In the above formula (A2), R 12 may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic ring structure.

[0050] In the above formula (A2), when Z is an ester group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is preferably a group represented by -NH-CO-NH 2 or a group represented by the above formula (W1). When Z is an amide group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, W is preferably a group represented by -CO-R 13 , and R 13 preferably has 1 to 2 carbon atoms.

[0051] The above component (A2) is not particularly limited, and examples thereof include diacetoneacrylamide, [2-(2-oxo-2-imidazolidinyl)ethyl] 2-methylpropenoate, and N-[2-(2-oxoimidazolidin-3-yl)ethyl]methacrylamide. Among these, from the viewpoint of durable water repellency, the above component (A2) is preferably diacetoneacrylamide or [2-(2-oxo-2-imidazolidinyl)ethyl] 2-methylpropenoate.

[0052] The above component (A2) may be used alone or in combination of two or more.

[0053] In the acrylic compound, the content ratio of the structural unit derived from the component (A1) and the structural unit derived from the component (A2) is preferably such that the ratio (A1) / (A2) of the mass of the component (A1) to be blended and the mass of the component (A2) is from 100 / 0 to 70 / 30, more preferably from 99.9 / 0.1 to 70 / 30, still more preferably from 99.8 / 0.2 to 80 / 20, and particularly preferably from 99.7 / 0.3 to 90 / 10. When (A1) / (A2) is within the above range, the durable water repellency and water repellency are better.

[0054] The total mass of the component (A1) to be blended and the component (A2) is preferably 60 to 100% by mass, more preferably 70 to 99% by mass, still more preferably 80 to 98% by mass, based on the total amount of the monomer components constituting the acrylic compound.

[0055] From the viewpoint of peel strength, the acrylic compound preferably contains, in addition to the component (A1) and the optional component (A2), at least one monomer (A3) (hereinafter also referred to as the "component (A3)") of vinyl chloride and vinylidene chloride as a monomer component.

[0056] From the viewpoint of maintaining the texture of the textile product, vinyl chloride is preferred as the component (A3).

[0057] From the viewpoints of water repellency, durable water repellency and peel strength, the mass of the component (A3) to be blended is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass in total of the mass of the component (A1) to be blended and the mass of the component (A2). From the viewpoints of water repellency, durable water repellency and texture, the mass of the component (A3) to be blended is preferably 100 parts by mass or less, more preferably 75 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, based on 100 parts by mass in total of the mass of the component (A1) to be blended and the mass of the component (A2).

[0058] Acrylic compounds, in terms of being able to improve the emulsion stability during emulsion polymerization or dispersion polymerization and in the composition after polymerization, in addition to component (A1) and optional component (A2), preferably contain, as a monomer component, at least one reactive emulsifier (A4) (hereinafter also referred to as "component (A4)") selected from a compound represented by the following general formula (A4-1) with an HLB of 7 to 18, a compound represented by the following general formula (A4-2) with an HLB of 7 to 18, and a compound (A4-3) obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group.

[0059] [Chemical formula] [In formula (A4-1), R 3 is hydrogen or a methyl group, X is a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.]

[0060] [Chemical formula] [In formula (A4-2), R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y 2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.]

[0061] In the present application, the "reactive emulsifier" refers to an emulsifying and dispersing agent having radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in the molecule, which can be copolymerized with a monomer such as a (meth)acrylate ester.

[0062] Also, "HLB" refers to the HLB value calculated by the Griffin method, considering the ethyleneoxy group in the reactive emulsifier as a hydrophilic group.

[0063] The HLB of the compounds of the above (A4-1) to (A4-3) is 7 to 18, and in terms of the emulsion stability during the emulsion polymerization or dispersion polymerization of the acrylic compound and in the composition after polymerization (hereinafter simply referred to as emulsion stability), 9 to 15 is preferable. Further, from the viewpoint of the storage stability of the water repellent composition, it is more preferable to use in combination two or more reactive emulsifiers (A4) having different HLB within the above range.

[0064] In the above general formula (A4-1), R 3 is hydrogen or a methyl group, and a methyl group is more preferable in terms of copolymerizability with the component (A1) and / or the component (A2). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and in terms of the emulsion stability of the acrylic compound, a linear alkylene group having 2 to 3 carbon atoms is more preferable. Y 1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. For the type, combination and number of added alkyleneoxy groups in Y 1 , they can be appropriately selected so as to be within the above HLB range. Further, when there are two or more alkyleneoxy groups, they can have a block addition structure or a random addition structure.

[0065] As the compound represented by the above general formula (A4-1), the compound represented by the following general formula (A4-1-1) is preferable.

[0066]

Chemical formula

[0067] In the compound represented by the above general formula (A4-1-1), R 3is a hydrogen or methyl group, and a methyl group is more preferable in terms of copolymerizability with the component (A1) and / or the component (A2). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferable in terms of the emulsion stability of the acrylic compound. A 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. A 1 Regarding the type and combination of A 1 O and the number m of A 1 O, they can be appropriately selected so as to be within the above HLB range. In terms of the emulsion stability of the acrylic compound, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, the m A

[0068] The reactive emulsifier represented by the general formula (A4-1-1) can be obtained by a conventionally known method and is not particularly limited. Moreover, it can be more easily obtained from commercially available products. For example, "Latemul PD-420", "Latemul PD-430", "Latemul PD-450", etc. manufactured by Kao Corporation can be mentioned.

[0069] In the above general formula (A4-2), R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group. Examples of the unsaturated hydrocarbon group include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, a heptadecatrienyl group, etc. In terms of the emulsion stability of the acrylic compound, R 4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0070] Y 2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. Y 2Regarding the type, combination, and number of added alkyleneoxy groups, they can be appropriately selected so as to be within the above HLB range. Further, when there are two or more types of alkyleneoxy groups, they can have a block addition structure or a random addition structure. From the viewpoint of the emulsion stability of the acrylic compound, the alkyleneoxy group is more preferably an ethyleneoxy group.

[0071] As the compound represented by the above general formula (A4-2), a compound represented by the following general formula (A4-2-1) is preferable.

[0072] [Chemical formula] [In formula (A4-2-1), R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms with a polymerizable unsaturated group, A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms, n can be appropriately selected so as to be within the above HLB range, specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A 2 O may be the same or different.]

[0073] R in the compound represented by the above general formula (A4-2-1) 4 is the same as R in the above-described general formula (A4-2). 4 Examples thereof can be given.

[0074] A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms. From the viewpoint of the emulsion stability of the acrylic compound, regarding the type and combination of A 2 O and the number of n, they can be appropriately selected so as to be within the above HLB range. From the viewpoint of the emulsion stability of the acrylic compound, A 2 O is more preferably an ethyleneoxy group, n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14. When n is 2 or more, n A 2 O may be the same or different. Further, A 2When there are two or more types of O, they can have a block addition structure or a random addition structure.

[0075] The reactive emulsifier represented by the above general formula (A4-2-1) can be synthesized, for example, by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group, but is not limited thereto. For example, it can be synthesized by using an alkali catalyst such as caustic soda or caustic potassium and adding a predetermined amount of alkylene oxide at 120 to 170 °C under pressure.

[0076] The phenol having the corresponding unsaturated hydrocarbon group includes, in addition to industrially produced pure products or mixtures, those existing as pure products or mixtures extracted and purified from plants and the like. For example, 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc., which are extracted from the shells of cashew nuts and collectively called cardanol, can be mentioned.

[0077] Compound (A4-3) is obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having an HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group. Examples of the oil or fat having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids which may contain hydroxy unsaturated fatty acids (such as palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one hydroxy unsaturated fatty acid (such as ricinoleic acid, ricinelaidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of the emulsion stability of the acrylic compound, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferred, an alkylene oxide adduct having 2 to 4 carbon atoms of castor oil (triglyceride of a fatty acid containing ricinoleic acid) is more preferred, and an ethylene oxide adduct of castor oil is even more preferred. Further, the number of moles of the added alkylene oxide can be appropriately selected so as to be within the above HLB range, and from the viewpoint of the emulsion stability of the acrylic compound, 20 to 50 moles is more preferred, and 25 to 45 moles is even more preferred. When two or more kinds of alkylene oxides are used, they can have a block addition structure or a random addition structure.

[0078] Compound (A4-3) can be synthesized, for example, by adding an alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, but is not limited thereto. For example, it can be synthesized by adding a predetermined amount of an alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, that is, castor oil, under pressure at 120 to 170 ° C using an alkali catalyst such as sodium hydroxide or potassium hydroxide.

[0079] The monomer composition ratio of the above (A4) component in the acrylic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass, based on the total amount of the monomer components constituting the acrylic compound, from the viewpoint of improving water repellency and emulsion stability in the emulsion polymerization or dispersion polymerization of the acrylic compound and in the composition after polymerization.

[0080] In terms of improving durable water repellency, the acrylic compound may contain, in addition to the (A1) component and the optional (A2) component, at least one second (meth)acrylic acid ester monomer (A5) (hereinafter also referred to as "A5 component") selected from the group consisting of a monomer represented by the following general formula (A5-1), a monomer represented by the following general formula (A5-2), a monomer represented by the following general formula (A5-3), and a monomer represented by the following general formula (A5-4) as a monomer component.

[0081]

Chemical formula

[0082]

Chemical formula

[0083]

Chemical formula

[0084] [Chemical formula] [In formula (A5-4), R 10 is hydrogen or a methyl group, p is an integer of 2 or more, S is a (p + 1)-valent organic group, and T is a monovalent organic group having a polymerizable unsaturated group.

[0085] The monomer of the above (A5-1) is a (meth) acrylic acid ester monomer having a monovalent linear hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth) acryloyloxy group in the ester moiety. From the viewpoint of being able to react with a crosslinking agent, the monovalent linear hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When an acrylic compound containing the monomer of (A5-1) having a group capable of reacting with these crosslinking agents is treated on a fiber product together with a crosslinking agent, the durability and water repellency can be improved while maintaining the texture of the obtained fiber product. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0086] The above linear hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the linear hydrocarbon group may further have a substituent in addition to the above functional group. Among them, in terms of being able to improve the durability and water repellency, it is preferably linear and / or a saturated hydrocarbon group.

[0087] Specific monomers of (A5-1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, etc. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferable in terms of improving the durable water repellency. Further, dimethylaminoethyl (meth)acrylate is preferable in terms of improving the texture.

[0088] From the viewpoint of water repellency, the mass of the (A5-1) component to be blended is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass in total of the mass of the (A1) component and the mass of the (A2) component to be blended. From the viewpoint of water repellency, the mass of the (A5-1) component to be blended is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass in total of the mass of the (A1) component and the mass of the (A2) component to be blended.

[0089] The monomer of (A5-2) above is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group with 1 to 11 carbon atoms in the ester moiety. Examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group, and a dicyclopentanyl group. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group is selected such that the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less. Further, from the viewpoint of improving the durable water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to the ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and in the case of alicyclic, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific monomers include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Among them, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable in terms of improving the durable water repellency.

[0090] From the viewpoint of water repellency, the mass of the component (A5-2) to be blended is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass in total of the mass of the component (A1) and the mass of the component (A2) to be blended. From the viewpoint of water repellency, the mass of the component (A5-2) to be blended is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass in total of the mass of the component (A1) and the mass of the component (A2) to be blended.

[0091] The monomer of the above (A5-3) is a methacrylic acid ester monomer in which a monovalent linear hydrocarbon group having 1 to 4 carbon atoms without substitution is directly bonded to the ester bond of the ester moiety. As the linear hydrocarbon group having 1 to 4 carbon atoms, a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the linear hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and the like. Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Among them, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable in terms of improving durable water repellency.

[0092] From the viewpoint of water repellency, the mass of the (A5-3) component to be blended is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass in total of the mass of the (A1) component and the mass of the (A2) component to be blended. From the viewpoint of water repellency, the mass of the (A5-3) component to be blended is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass in total of the mass of the (A1) component and the mass of the (A2) component to be blended.

[0093] The monomer of the above (A5-4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. A polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule, where T in the above general formula (A5-4) is a (meth)acryloyloxy group, is preferred. In formula (A5-4), the p Ts may be the same or different. Specific compounds include, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. These monomers may be used alone or in combination of two or more. Among them, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred in terms of improving the durable water repellency.

[0094] From the perspective of water repellency, the mass of the (A5-4) component to be blended is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass in total of the mass of the (A1) component and the mass of the (A2) component to be blended. From the perspective of water repellency, the mass of the (A5-4) component to be blended is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass in total of the mass of the (A1) component and the mass of the (A2) component to be blended.

[0095] From the perspectives of water repellency and texture, the total composition ratio of the monomers of the above (A5) component in the acrylic compound is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, based on the total amount of the monomer components constituting the acrylic compound.

[0096] The mass of the component (A5) to be blended is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, from the viewpoint of water repellency, based on 100 parts by mass in total of the mass of the component (A1) to be blended and the mass of the component (A2). The mass of the component (A5) to be blended is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, from the viewpoint of water repellency, based on 100 parts by mass in total of the mass of the component (A1) to be blended and the mass of the component (A2).

[0097] In addition to the component (A1) and the optional component (A2), the acrylic compound can contain a monofunctional monomer (A6) copolymerizable therewith (hereinafter also referred to as "component (A6)") within a range not impairing the effects of the present invention.

[0098] Examples of the component (A6) include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group other than the above components (A1), (A2), and (A5), (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, and vinyl monomers other than the fluorine-free component (A3) such as ethylene and styrene. The (meth)acrylic acid ester having a hydrocarbon group other than the components (A1), (A2), and (A5) may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group in the hydrocarbon group, and may have a substituent other than a group capable of reacting with a crosslinking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Examples of the (meth)acrylic acid ester other than the components (A1), (A2), and (A5) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate. Among them, (meth)acryloylmorpholine is more preferable in terms of improving the peel strength of the obtained fiber product coating.

[0099] The mass of the component (A6) to be blended is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, from the viewpoint of water repellency, based on 100 parts by mass in total of the mass of the component (A1) to be blended and the mass of the component (A2). The mass of the monomer of the above (A6) to be blended is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, from the viewpoint of water repellency, based on 100 parts by mass in total of the mass of the component (A1) to be blended and the mass of the component (A2).

[0100] It is preferable that the acrylic compound has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent, as it improves the durable water repellency. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, it is preferable that the acrylic compound has an amino group as it improves the texture.

[0101] The weight average molecular weight of the acrylic compound is preferably 30,000 or more. When the weight average molecular weight is 30,000 or more, the water repellency tends to be further improved. Furthermore, the weight average molecular weight of the acrylic compound is more preferably 50,000 or more. In this case, the water repellency can be more sufficiently exhibited. The upper limit of the weight average molecular weight of the acrylic compound is preferably about 5,000,000.

[0102] The weight average molecular weight of the acrylic compound refers to the value in terms of standard polystyrene conversion, measured using tetrahydrofuran as the eluent under the conditions of a column temperature of 40 °C and a flow rate of 1.0 ml / min with a GPC apparatus (GPC "HLC-8020" manufactured by Tosoh Corporation). In addition, as the column, three columns with the trade names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation are connected and used.

[0103] The melt viscosity of the acrylic compound at 105°C is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, it tends to be easier to maintain good texture. Also, when the melt viscosity of the acrylic compound is 1000 Pa·s or less, when the acrylic compound is emulsified or dispersed to form a water repellent composition, precipitation or sedimentation of the acrylic compound can be suppressed, so the storage stability of the water repellent composition tends to be easily maintained well. Incidentally, the melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, while exhibiting sufficient water repellency, the texture becomes even better.

[0104] The "melt viscosity at 105°C" means that 1 g of a non-fluorine-based polymer is placed in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation), held at 105°C for 6 minutes, and the viscosity measured when a load of 100 kg·f / cm 2 is applied by a plunger.

[0105] (silicone-based compound) The silicone-based compound is, for example, at least one of a silicone resin and a silicone oil. Among such silicone-based compounds, a silicone resin is preferred from the viewpoint of water repellency. The silicone-based compound may be used alone or in combination of two or more.

[0106] The silicone resin may be an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT or MDTQ as a constituent component, being solid at 25°C and having a three-dimensional structure. Here, M, D, T and Q represent (R'') 3 SiO 0.5 units, (R'') 2 SiO units, R''SiO 1.5 units and SiO 2 units respectively. R'' represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

[0107] Silicone resins are generally known as MQ resins, MT resins, or MDT resins, and may also have moieties denoted as MDQ, MTQ, or MDTQ.

[0108] Silicone resins can also be obtained as a solution in which they are dissolved in a suitable solvent. Examples of the solvent include relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures of these solvents.

[0109] Examples of solutions of silicone resins include KF7312J (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and decamethylcyclopentasiloxane), KF7312F (trimethylsilyl group-containing polysiloxane:octamethylcyclotetrasiloxane), KF9021L (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and low-viscosity methylpolysiloxane), KF7312L (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and low-viscosity methylpolysiloxane), etc., which are commercially available from Shin-Etsu Chemical Co., Ltd.

[0110] Examples of silicone resins alone include MQ-1600 solid Resin (trimethylsilyl group-containing polysiloxane), MQ-1640 Flake Resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane), etc., which are commercially available from Toray Dow Corning Co., Ltd. The above commercial products contain trimethylsilyl group-containing polysiloxane and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0111] Silicone oil is a linear organopolysiloxane, which may have organic groups on at least one of the side chains and terminals of the organopolysiloxane. As such silicone oil, the same as hydrophobic silicone oil and functionalized silicone oil can be used. For example, straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, etc.; modified silicone oils such as amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, alkylaralkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, higher aliphatic amide-modified silicone oil, etc. can be mentioned.

[0112] Examples of amino-modified silicone oil include compounds having organic groups containing amino groups and / or imino groups on at least one of the side chains and terminals of organopolysiloxane. Such organic groups include organic groups represented by -R-NH 2 and organic groups represented by -R-NH-R’-NH 2 . Examples of R and R’ include divalent groups such as ethylene group and propylene group. Some or all of the amino groups and / or imino groups may be blocked amino groups and / or imino groups. The blocked amino groups and / or imino groups can be obtained, for example, by treating the amino groups and / or imino groups with a blocking agent. Examples of the blocking agent include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, aliphatic monoisocyanates having 1 to 22 carbon atoms, etc.

[0113] From the viewpoint of water repellency, the functional group equivalent of the amino-modified silicone oil is preferably 100 to 20000 g / mol, more preferably 150 to 12000 g / mol, and still more preferably 200 to 4000 g / mol.

[0114] The amino-modified silicone oil is preferably liquid at 25°C. The kinematic viscosity of the amino-modified silicone oil at 25°C is preferably 10 to 100,000 mm 2 / s, more preferably 10 to 30,000 mm 2 / s, and even more preferably 10 to 5,000 mm 2 / s. When the kinematic viscosity at 25°C is greater than 100,000 mm 2 / s, the viscosity is too high and the workability tends to deteriorate. The kinematic viscosity at 25°C means the value measured by the method described in JIS K2283:2000 (Ubbelohde viscometer).

[0115] As the amino-modified silicone oil, it can be easily obtained as a commercial product. Examples of commercial products include KF8005, KF-868, KF-864, KF-393, KF-8021 (all are trade names manufactured by Shin-Etsu Chemical Co., Ltd.), TSF-4709, XF42-B1989 (trade name manufactured by Momentive Performance Materials Japan Co., Ltd.), BY16-872, SF-8417, BY16-853U, BY16-892 (all are trade names manufactured by Toray Dow Corning Co., Ltd.), KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), WACKER (registered trademark) FINISH WR 301 (manufactured by Asahi Kasei Wacker Silicone), etc.

[0116] In addition, silicone oils other than amino-modified silicone oil can also be easily obtained as commercially available products. Examples of commercially available products include KF-101 (trade name, epoxy-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-3701E (trade name, carboxyl-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.), SF8428 (trade name, carbinol-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.), KF-9901 (trade name, methylhydrogen silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-715 (trade name, higher fatty acid ester-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.), KF-96-3000cp (trade name, dimethyl silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.), SF8416 (trade name, alkyl-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.), SH203 (trade name, alkyl aralkyl-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.), SF8410 (trade name, polyether-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.), and the like.

[0117] The silicone-based compound may be an organo-modified silicone represented by the following general formula (1). In the following general formula (1), each structural unit may be a block, random, or arranged alternately.

[0118] [Chemical formula] [In formula (1), R 20 , R 21 and R 22 are each independently a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R 23 is a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 8 to 40 carbon atoms, and R 30 , R 31 , R 32 , R 33 , R 34 and R 35is, independently of each other, a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a is an integer of 0 or more, b is an integer of 1 or more, (a + b) is 10 to 200, and when a is 2 or more, a plurality of Rs exist 20 and R 21 may be the same or different from each other, and when b is 2 or more, a plurality of Rs exist 22 and R 23 may be the same or different from each other.]

[0119] In the organo-modified silicone, the alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. In terms of being easy to manufacture industrially and being easily available, R 20 、R 21 and R 22 are each independently preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0120] Examples of the hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring include an aralkyl group having 8 to 40 carbon atoms, a group represented by the following general formula (2) or (3), and the like.

[0121]

Chemical formula

[0122] The above-mentioned alkylene group may be linear or branched.

[0123]

Chemical formula

[0124] The above alkylene group may be linear or branched.

[0125] Examples of the above aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylethyl group, and the like. Among them, a phenylethyl group and a phenylpropyl group are preferable in terms of being easily manufactured industrially and being easily available.

[0126] In the group represented by the above general formula (2), in terms of being easily manufactured industrially and being easily available, R 40 is preferably an alkylene group having 2 to 4 carbon atoms, c is preferably 0 or 1, and more preferably 0.

[0127] In the group represented by the above general formula (3), in terms of being easily manufactured industrially and being easily available, R 42 is preferably an alkylene group having 2 to 4 carbon atoms, d is preferably 0 or 1, and more preferably 0.

[0128] As the above hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, in terms of being easily manufactured industrially and being easily available, the above aralkyl group having 8 to 40 carbon atoms and the group represented by the above general formula (2) are preferable, and in terms of being able to improve water repellency, the above aralkyl group having 8 to 40 carbon atoms is more preferable.

[0129] The above alkyl group having 8 to 40 carbon atoms may be linear or branched. Examples of the alkyl group having 8 to 40 carbon atoms include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a myristyl group, a cetyl group, a stearyl group, a behenyl group, a hexacosyl group, an octacosyl group, a triacontyl group, a dotriacontyl group, and the like. As the alkyl group having 8 to 40 carbon atoms, an alkyl group having 12 to 36 carbon atoms is preferable, and an alkyl group having 16 to 34 carbon atoms is more preferable in terms of improving water repellency. In addition, the smaller the number of carbon atoms in the alkyl group, the more excellent the chalk mark tends to be. Also, the larger the number of carbon atoms in the alkyl group, the more excellent the water repellency tends to be. Further, when the number of carbon atoms exceeds 40, the stability of the dispersion tends to decrease. Furthermore, when the number of carbon atoms is less than 8, the water repellency tends to be poor.

[0130] In the organo-modified silicone, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms. In terms of being easy to manufacture industrially and being easily available, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group among them.

[0131] In the organo-modified silicone, a is an integer of 0 or more. In terms of being easy to manufacture industrially, being easily available, and having more excellent peel strength, a is preferably 40 or less, and more preferably 30 or less.

[0132] In the organo-modified silicone, (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the silicone itself tends to be easier to produce and handle.

[0133] The organo-modified silicone can be synthesized by a conventional method, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an aromatic compound having a vinyl group and / or an α-olefin.

[0134] Examples of silicones having a SiH group include methylhydrogensilicones having a degree of polymerization of 10 to 200, and copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred because they are easy to produce industrially and are readily available.

[0135] The aromatic compound having a vinyl group is represented by the formula (1) R 23 In the above formula, it is a compound from which a hydrocarbon group having an aromatic ring and a carbon number of 8 to 40 is derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0136] The above α-olefin is represented by the formula (1) R 23It is a compound derived from an alkyl group having 8 to 40 carbon atoms. Examples of the α-olefin include α-olefins having 8 to 40 carbon atoms such as 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexacosene (C26), 1-octacosene (C28), 1-triacontene (C30), 1-dotriacontene (C32), and the like.

[0137] The above hydrosilylation reaction may be carried out by reacting the silicone having the above SiH group with the aromatic compound having the above vinyl group and the above α-olefin stepwise or at once in the presence of a catalyst as necessary.

[0138] The amounts of the silicone having an SiH group, the aromatic compound having a vinyl group, and the α-olefin used in the hydrosilylation reaction can be appropriately selected according to the SiH group equivalent of the silicone having an SiH group, the number average molecular weight, or the like.

[0139] Examples of the catalyst used in the hydrosilylation reaction include compounds such as platinum and palladium, and platinum compounds are particularly preferred. Examples of the platinum compound include platinum(IV) chloride and the like.

[0140] The reaction conditions of the hydrosilylation reaction are not particularly limited and can be appropriately adjusted. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C.

[0141] Also, the hydrosilylation reaction is preferably carried out in an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, and the like. The reaction proceeds even without a solvent, but a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate, and the like.

[0142] As non-fluorine-based water-repellent components, from the viewpoints of water repellency and chalk marks, it is preferable to use the above acrylic-based compound and the above silicone-based compound in combination. The mass ratio of the acrylic-based compound (α) to the silicone-based compound (β) is not particularly limited. For example, when the silicone-based compound (β) is a silicone resin, with the total of the acrylic-based compound (α) and the silicone-based compound (β) being 100 parts by mass, the silicone-based compound (β) may account for 1 to 99 parts by mass. Preferably it is 5 to 98 parts by mass, more preferably 10 to 97 parts by mass, still more preferably 15 to 95 parts by mass. When the proportion of the silicone-based compound (β) is within this range, it will be excellent in water repellency and Bundesmann water repellency after abrasion. Or, when the silicone-based compound (β) is an organo-modified silicone, with the total of the acrylic-based compound (α) and the silicone-based compound (β) being 100 parts by mass, the silicone-based compound (β) may account for 10 to 90 parts by mass. Preferably it is 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, still more preferably 20 to 60 parts by mass. When the proportion of the silicone-based compound (β) is within this range, it will be excellent in water repellency and less likely to generate chalk marks.

[0143] (wax-based compound) The wax-based compound is, for example, at least one selected from paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, animal and plant waxes, and mineral waxes, and from the viewpoints of water repellency, durable water repellency, and texture, paraffin wax is preferable.

[0144] The wax-based compound may be, for example, one or both of normal alkanes and normal alkenes. From the viewpoints of water repellency, durable water repellency, and texture, the wax-based compound is preferably a normal alkane.

[0145] Examples of the normal alkane include at least one selected from tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane. From the viewpoints of water repellency, durable water repellency, and texture, the normal alkane is preferably triacontane, hentriacontane, or dotriacontane.

[0146] Examples of the normal alkene include at least one selected from 1 - eicosene, 1 - docosene, 1 - tricosene, 1 - tetracosene, 1 - pentacosene, 1 - hexacosene, 1 - heptacosene, 1 - octacosene, nonacosene, triacontene, hentriacontene, dotriacontene, tritriacontene, tetratriacontene, pentatriacontene, and hexatriacontene. From the viewpoints of water repellency, durable water repellency, and texture, the normal alkene is preferably at least one of triacontene, hentriacontene, and dotriacontene.

[0147] The number of carbon atoms of the wax - based compound is not particularly limited, but may be 20 to 60, and preferably 25 to 45 from the viewpoints of water repellency, durable water repellency, and texture.

[0148] The weight - average molecular weight of the wax - based compound is not particularly limited, but may be 300 to 850, and preferably 300 to 700 from the viewpoints of water repellency, durable water repellency, and texture.

[0149] The melting point of the wax - based compound is preferably 35 to 90°C, more preferably 40 to 85°C, still more preferably 45 to 80°C, and even more preferably 50 to 75°C from the viewpoints of good water repellency and durable water repellency, particularly good water repellency and durable water repellency against cotton. The melting point of the wax - based compound refers to the value measured by the same method as JIS K2235 - 1991.

[0150] The penetration of the wax-based compound is not particularly limited, but for example, it may be 30 or less, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less from the viewpoints of water repellency and durable water repellency. The penetration of the wax-based compound is not particularly limited, but for example, it may be 0.1 or more and may be 1 or more. The penetration of the wax-based compound refers to the value measured by the same method as JIS K2235-1991.

[0151] (Urethane-based compound) The urethane-based compound is, for example, a reaction product of an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound. More specifically, for example, (U1) an aliphatic polyisocyanate derivative having an average isocyanate group number of 2 or more, (U2) a long-chain active hydrogen compound having a hydrocarbon group and an active hydrogen group with 12 to 30 carbon atoms, (U3) a cationic active hydrogen compound having an active hydrogen group and a cationic group, (U4) an acid compound that forms a salt with a cationic group, may be a reaction product thereof. Here, the concentration of the hydrocarbon group may be 30% or more and 85% or less. Further, the aliphatic polyisocyanate derivative may contain an isocyanurate derivative of an aliphatic polyisocyanate. Furthermore, in the cationic active hydrogen compound, the cationic group may be a tertiary amino group, the active hydrogen group may be a hydroxyl group, and the cationic active hydrogen compound may have two or more hydroxyl groups per molecule. When the urethane-based compound is a reaction product obtained using a long-chain active hydrogen compound and the concentration of the hydrocarbon group is at a predetermined ratio, it is likely to have excellent water repellency. Also, when the urethane-based compound is a reaction product obtained using a cationic active hydrogen compound, for example, the affinity with fibers is improved, and thereby the washing durability is likely to be improved.

[0152] Examples of the aliphatic polyisocyanate that constitutes the aliphatic polyisocyanate derivative (U1) include aliphatic diisocyanates such as hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. In the present application, the term "aliphatic polyisocyanate" is a concept that includes alicyclic polyisocyanates.

[0153] Examples of the alicyclic polyisocyanate include alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′-, 2,4′- or 2,2′-methylenebis(cyclohexyl isocyanate) or a mixture thereof (H12MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

[0154] The aliphatic polyisocyanate is preferably one or both of hexamethylene diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter simply referred to as bis(isocyanatomethyl)cyclohexane), and more preferably hexamethylene diisocyanate.

[0155] Examples of the aliphatic polyisocyanate derivatives include, for example, multimers of the above-described aliphatic polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (e.g., allophanate derivatives produced by the reaction of the above-described aliphatic polyisocyanates with monohydric alcohols or dihydric alcohols, etc.), polyol derivatives (e.g., polyol derivatives (alcohol adducts, preferably trimethylolpropane adducts) produced by the reaction of the above-described aliphatic polyisocyanates with trihydric alcohols (e.g., trimethylolpropane, etc.)), biuret derivatives (e.g., biuret derivatives produced by the reaction of the above-described aliphatic polyisocyanates with water or amines, etc.), urea derivatives (e.g., urea derivatives produced by the reaction of the above-described aliphatic polyisocyanates with diamines, etc.), oxadiazinetrione derivatives (e.g., oxadiazinetriones produced by the reaction of the above-described aliphatic polyisocyanates with carbon dioxide gas, etc.), carbodiimide derivatives (carbodiimide derivatives produced by the decarboxylation condensation reaction of the above-described aliphatic polyisocyanates, etc.), uretdione derivatives, uretonimine derivatives, and the like.

[0156] The aliphatic polyisocyanate derivative is preferably at least one of an isocyanurate derivative, a trimethylolpropane adduct, an allophanate derivative, and a biuret derivative, and more preferably an isocyanurate derivative. When the aliphatic polyisocyanate derivative contains an isocyanurate derivative, the texture becomes good.

[0157] The aliphatic polyisocyanate derivative is more preferably at least one of an isocyanurate derivative of hexamethylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, a biuret derivative of hexamethylene diisocyanate, and an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, and still more preferably an isocyanurate derivative of hexamethylene diisocyanate.

[0158] The aliphatic polyisocyanate derivative can be used alone or in combination of two or more. Preferably, it includes the use of an isocyanurate derivative of hexamethylene diisocyanate alone, or the combined use of an isocyanurate derivative of hexamethylene diisocyanate and at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate. In this case, the blending ratio of the isocyanurate derivative of hexamethylene diisocyanate is, for example, 60 parts by mass or more, preferably 70 parts by mass or more, and, for example, 85 parts by mass or less, based on 100 parts by mass of the total amount of the isocyanurate derivative of hexamethylene diisocyanate and at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate. Also, the blending ratio of at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate is, for example, 15 parts by mass or more, and, for example, 40 parts by mass or less, preferably 30 parts by mass or less.

[0159] Aliphatic polyisocyanate derivatives can be produced by known methods.

[0160] The average isocyanate functionality of the aliphatic polyisocyanate derivative is 2 or more, preferably 2.5, more preferably 2.9, and, for example, 3.8 or less. If the above average isocyanate functionality is at least the above lower limit, the water repellency can be further improved. The average isocyanate functionality is calculated by the following formula (1) from the isocyanate group concentration A, solid content concentration B of the aliphatic polyisocyanate derivative, and the number average molecular weight C of gel permeation chromatography measured under the following apparatus and conditions. Further, when two or more kinds of aliphatic polyisocyanate derivatives are used in combination, the above average isocyanate functionality is calculated from the weight ratio of the aliphatic polyisocyanate derivatives and their average isocyanate functional groups.

[0161] Average isocyanate functional groups = A / B × C / 42.02 (1) (In the formula, A represents the isocyanate group concentration of the aliphatic polyisocyanate derivative, B represents the solid content concentration, and C represents the number average molecular weight.)

[0162] (Measurement conditions for number average molecular weight) Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: TSKgel G1000HXL, TSKgel G2000HXL, and TSKgel G3000HXL (manufactured by Tosoh Corporation) connected in series Detector: Differential refractometer Injection volume: 100 μL Eluent: Tetrahydrofuran Flow rate: 0.8 mL / min Temperature: 40 °C Calibration curve: Standard polyethylene oxide in the range of 106 to 22450 (manufactured by Tosoh Corporation, trade name: TSK standard polyethylene oxide)

[0163] The long-chain active hydrogen compound has a hydrocarbon group with 12 to 30 carbon atoms and an active hydrogen group that reacts with an aliphatic polyisocyanate derivative.

[0164] The hydrocarbon group with 12 to 30 carbon atoms may be, for example, a linear or branched saturated hydrocarbon group with 12 to 30 carbon atoms (such as an alkyl group, etc.), or a linear or branched unsaturated hydrocarbon group with 12 to 30 carbon atoms (such as an alkenyl group, etc.).

[0165] The active hydrogen group may be, for example, a hydroxyl group.

[0166] The long-chain active hydrogen compound having such a hydrocarbon group and an active hydrogen group may be, for example, at least one of a linear saturated hydrocarbon group-containing active hydrogen compound, a branched saturated hydrocarbon group-containing active hydrogen compound, a linear unsaturated hydrocarbon group-containing active hydrogen compound, and a branched unsaturated hydrocarbon group-containing active hydrogen compound.

[0167] The linear saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear saturated hydrocarbon group with 12 to 30 carbon atoms, and examples include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, eicosanol, etc., and linear saturated hydrocarbon group-containing sorbitan esters such as sorbitan tristearate, etc.

[0168] The branched saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched saturated hydrocarbon group with 12 to 30 carbon atoms, and examples include branched saturated hydrocarbon group-containing alcohols such as isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, isoeicosyl alcohol, etc.

[0169] The linear unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear unsaturated hydrocarbon group having 12 to 30 carbon atoms. Examples thereof include linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacoseneyl alcohol, octacoseneyl alcohol, and the like.

[0170] The branched-chain unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched-chain unsaturated hydrocarbon group having 12 to 30 carbon atoms. Examples thereof include phytol and the like.

[0171] The long-chain active hydrogen compound is preferably one or both of a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound. The long-chain active hydrogen compound can be used alone or in combination of two or more.

[0172] When the long-chain active hydrogen compound is used alone, preferably, the linear saturated hydrocarbon group-containing active hydrogen compound is used alone, more preferably, the linear saturated hydrocarbon group-containing alcohol is used alone, and still more preferably, stearyl alcohol is used alone. When two or more long-chain active hydrogen compounds are used in combination, preferably, the linear saturated hydrocarbon group-containing active hydrogen compound and the linear unsaturated hydrocarbon group-containing active hydrogen compound are used in combination, more preferably, the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol are used in combination, or the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol are used in combination.

[0173] When a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. Further, the blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 60 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. If the blending ratio of the linear saturated hydrocarbon group-containing alcohol is at least the above lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the water repellency can be improved.

[0174] When a linear saturated hydrocarbon group-containing alcohol, a linear saturated hydrocarbon group-containing sorbitan ester, and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 30 parts by mass or more and, for example, 60 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. Further, the blending ratio of the linear saturated hydrocarbon group-containing sorbitan ester is, for example, 20 parts by mass or more and, for example, 50 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. Further, the blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass or more and, for example, 20 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol.

[0175] When two or more long-chain active hydrogen compounds are used in combination, it is more preferable to use a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol in combination, and particularly preferably, stearyl alcohol and oleyl alcohol are used in combination.

[0176] The cationic active hydrogen compound has both an active hydrogen group and a cationic group. The cationic active hydrogen compound can be used alone or in combination of two or more.

[0177] As described above, the active hydrogen group is an active hydrogen group that reacts with the aliphatic polyisocyanate derivative, and examples thereof include a hydroxyl group. The cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule. Further, examples of the cationic group include a tertiary amino group. That is, the cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule as the active hydrogen group and a tertiary amino group as the cationic group. More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen group and a tertiary amino group as the cationic group. According to such a cationic active hydrogen compound, good dispersibility in water can be imparted, and a cationic group having an affinity for fibers can be introduced, so that the washing durability can be improved.

[0178] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine, and preferably, N-methyldiethanolamine.

[0179] The acid compound is a compound that forms a salt with a cationic group. Examples of the acid compound include one or both of organic acids and inorganic acids. Examples of the organic acid include acetic acid, lactic acid, tartaric acid, or malic acid, etc., preferably acetic acid or lactic acid, more preferably acetic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, or phosphoric acid, etc., preferably hydrochloric acid. The acid compound is preferably an organic acid. When the acid compound contains an organic acid, the acid volatilizes by heat treatment, resulting in a decrease in ionicity, an improvement in water resistance, and an improvement in water repellency. Also, when the acid volatilizes by heat treatment, the cationic group becomes more likely to adsorb to the fiber, and the washing durability can be improved. The acid compound can be used alone or in combination of two or more kinds.

[0180] By reacting the above-mentioned aliphatic polyisocyanate derivative with a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound, a urethane-based compound as a reaction product can be obtained. To react the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound, first, the long-chain active hydrogen compound is blended with the aliphatic polyisocyanate derivative, and the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound are reacted. At this time, for example, when the average number of isocyanate groups of the isocyanurate derivative of the aliphatic polyisocyanate is 3, the long-chain active hydrogen compound is preferably such that two isocyanate groups in the isocyanurate derivative of the aliphatic polyisocyanate are modified by the long-chain active hydrogen compound into a hydrocarbon group having 12 or more and 30 or less carbon atoms, and one isocyanate group in the isocyanurate derivative of the aliphatic polyisocyanate remains, and no unreacted isocyanurate derivative of the aliphatic polyisocyanate remains. Specifically, the long-chain active hydrogen compound is blended with the aliphatic polyisocyanate derivative such that the equivalent ratio of the isocyanate group to the active hydrogen group (isocyanate group / active hydrogen group) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less. Thereby, the molecular terminals of the reaction product of the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound (hereinafter referred to as the first intermediate reaction product) become a hydrocarbon group having 12 or more and 30 or less carbon atoms and an isocyanate group.

[0181] The above reaction is carried out under a nitrogen atmosphere. Also, the reaction conditions are such that the reaction temperature is, for example, 70°C or higher and 120°C or lower, and the reaction time is 1 hour or more and 6 hours or less. Also, the above reaction is carried out until the isocyanate concentration of the first intermediate reaction product reaches a predetermined calculated value. Incidentally, the isocyanate concentration can be measured by the n-dibutylamine method in accordance with JIS K-1556 using a potentiometric titration apparatus.

[0182] Also, in the above reaction, a known solvent (solvent) such as methyl ethyl ketone can be blended at an appropriate ratio.

[0183] Next, a cationic active hydrogen compound is added to the reaction solution containing the first intermediate reaction product, and the first intermediate reaction product is reacted with the cationic active hydrogen compound. At this time, the cationic active hydrogen compound is added to the first intermediate reaction product such that the equivalent ratio of the isocyanate group to the active hydrogen group of the cationic active hydrogen compound (isocyanate group / active hydrogen group) is, for example, 0.95 or more and, for example, 1.05 or less.

[0184] The above reaction is carried out under a nitrogen atmosphere. The reaction conditions are such that the reaction temperature is, for example, 70°C or higher and 120°C or lower, and the reaction time is 0.5 hours or more and 4 hours or less. Also, the above reaction is carried out until the reaction between the first intermediate reaction product and the cationic active hydrogen compound is complete. In the above reaction, a known solvent such as methyl ethyl ketone can also be added in an appropriate ratio. Thereby, a reaction product of the first intermediate reaction product and the cationic active hydrogen compound (hereinafter referred to as the second intermediate reaction product) is obtained. The second intermediate reaction product has a hydrocarbon group having 12 to 30 carbon atoms and a cationic group.

[0185] Next, an acid compound is added to the second intermediate reaction product. The blending ratio of the acid compound is, for example, 0.5 mol or more, preferably 3 mol or more, and, for example, 10 mol or less, preferably 4 mol or less, per 1 mol of the cationic group of the cationic active hydrogen compound. Thereby, the acid compound forms a salt with the cationic group of the second intermediate reaction product, and a reaction solution containing a reaction product of an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound (i.e., a urethane-based compound) is obtained. The above reaction product has a hydrocarbon group having 12 to 30 carbon atoms and a cationic group. Also, since the above reaction product has a hydrocarbon group having 12 to 30 carbon atoms, it can be self-dispersed (self-emulsified) in water without the use of a dispersant (emulsifier). In other words, the above reaction product can be internally emulsified.

[0186] Next, while maintaining the temperature of this reaction solution, for example, at 50°C or higher and 100°C or lower, water is added to this reaction solution to form an emulsion. Then, the solvent is removed from this reaction solution. As a result, an aqueous dispersion containing the above reaction product (i.e., the urethane-based compound) is obtained. The solid content concentration of the aqueous dispersion is, for example, 10% by mass or higher and, for example, 30% by mass or lower.

[0187] Since such a urethane-based compound is a reaction product obtained using a long-chain active hydrogen compound, it has excellent water repellency, as well as excellent oil repellency, oil resistance, and antifouling properties. Also, since such a urethane-based compound is a reaction product obtained using a cationic active hydrogen compound, its affinity with fibers is improved, and as a result, it has excellent washing durability against fibers.

[0188] In such a urethane-based compound, the concentration of the hydrocarbon group is 30% or higher and 85% or lower, preferably 50%. If the concentration of the hydrocarbon group is at least the above lower limit, the water repellency can be improved. Also, if the concentration of the hydrocarbon group is at most the above upper limit, the stability of the urethane-based compound can be improved. The concentration of the above hydrocarbon group can be calculated from the charged amounts of the respective components described above.

[0189] In the above description, first, an aliphatic polyisocyanate derivative and a long-chain active hydrogen compound are reacted to obtain a reaction solution containing a first intermediate reaction product. Next, the first intermediate reaction product and a cationic active hydrogen compound are reacted to obtain a reaction solution containing a second intermediate reaction product. Then, the second intermediate reaction product and an acid compound are reacted. However, the order of the reactions is not particularly limited. For example, it is also possible to react the aliphatic polyisocyanate derivative with the cationic active hydrogen compound first, and then react the long-chain active hydrogen compound with the acid compound. Also, it is possible to mix the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound together and react them.

[0190] (Dendrimer-based compound) The dendrimer-based compound may be, for example, a dendritic polymer compound having a radial and regularly branched structure from the center. As the dendritic polymer compound, those having a linear or branched hydrocarbon group having 1 or more carbon atoms at the terminal branch portion can be used to obtain water repellency.

[0191] As the dendritic polymer compound, for example, the "apolymer extender" disclosed in International Publication No. 2014 / 160906 can be used. For example, at least one kind of an isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate or a mixture thereof and at least one kind of an isocyanate-reactive compound selected from the following formula (Ia), (Ib) or (Ic) can be reacted to obtain a compound that can be used.

[0192] [Chemical formula]

[0193] In the above formula, R 50 is independently, each, -H, R 51 , -C(O)R 51 , -(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 52 , or, -(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 51 . n is independently, each, 0 to 20, m is independently, each, 0 to 20, and m + n exceeds 0. Also, R 51 is independently, each, a linear or branched alkyl group having 5 to 29 carbon atoms which may contain 1 or more unsaturated bonds, and R 52 is independently, each, -H, or a linear or branched alkyl group having 6 to 30 carbon atoms which may contain 1 or more unsaturated bonds.

[0194] In the formula (Ia), R 50 or R 52 at least one of them is -H.

[0195] In the above formula, R 53 are each independently -H, -R 51 , -C(O)R 51 , -(CH 2 CH 2 O(CH(CH 3 )CH 2 O) m R 52 , or -(CH 2 CH 2 O(CH(CH 3 )CH 2 OC(O)R 51 , and R 54 are each independently -H, or a linear or branched alkyl group having 6 to 30 carbon atoms which may contain one or more unsaturated bonds, -(CH 2 CH 2 O) n’ (CH(CH 3 )CH 2 O) m’ R 52 , or -(CH 2 CH 2 O(CH(CH 3 )CH 2 OC(O)R 51 , and n' are each independently 0 to 20, m' are each independently 0 to 20, and m + n is greater than 0.

[0196] In the formula (Ib), R 52 , R 53 or R 54 at least one of them is -H.

[0197] In the above formula, R 55 is -H, -C(O)R 51 , or -CH 2 C[CH 2 OR 50 3 . ​

[0198] In formula (Ic), at least one of R 55 or R 50 is -H.

[0199] The isocyanate group-containing compound is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified polyisocyanates such as dimers and trimers thereof. Commercially available products such as "DESMODURN-100" (manufactured by Bayer, trade name), "DURANATE THA-100" (manufactured by Asahi Kasei Corporation, trade name), and "DURANATE 24A-100" (manufactured by Asahi Kasei Corporation, trade name) can be used. Further, the reaction can be carried out, for example, at 80°C for 1 hour or more.

[0200] 2.1.2 Other Components The water-repellent treatment agent may contain, for example, in addition to the above non-fluorine-based water-repellent component, other components such as an aqueous medium and an emulsifier.

[0201] (Aqueous Medium) The aqueous medium may be water or a mixture of water and an organic solvent. The amount of the organic solvent may be, for example, 0.1% by mass or more and 30% by mass or less, or 0.1% by mass or more and 10% by mass or less with respect to the aqueous medium. The aqueous medium preferably consists only of water. The amount of the aqueous medium may be 30 to 99% by mass, or 50 to 90% by mass based on 100% by mass of the whole water-repellent treatment agent.

[0202] (Emulsifier) The water-repellent treatment agent may contain an emulsifier in order to improve the dispersibility of a non-fluorine-based water-repellent component or the like in the above solvent. The emulsifier may be at least one selected from among nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. From the viewpoint of water repellency, the emulsifier is preferably a nonionic surfactant alone or a combination of a nonionic surfactant and a cationic surfactant. In the combination of a nonionic surfactant and a cationic surfactant, the mass ratio of the nonionic surfactant to the cationic surfactant may be, for example, 99.5:0.5 to 50:50, or 99:1 to 90:10.

[0203] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, fatty acid alkanolamides, alkyl alkanolamides, acetylene glycols, oxyethylene adducts of acetylene glycols, polyethylene glycol polypropylene glycol block copolymers, and the like. Examples of anionic surfactants include sulfate salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkyl phenyl ether phosphates, and the like. Examples of cationic surfactants include amine salts, amide amine salts, quaternary ammonium salts, and imidazolinium salts. Specific examples include, but are not particularly limited to, amine salt type surfactants such as alkyl amine salts, polyoxyethylene alkyl amine salts, alkyl amide amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt type surfactants such as alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl pyridinium salts, alkyl isoquinolinium salts, and benzethonium chloride. Examples of amphoteric surfactants include alkyl amine oxides, alanines, imidazolinium betaines, amide betaines, betaine acetates, and the like. Specifically, long-chain amine oxides, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethyl aminoacetate betaine, fatty acid amide propyl dimethyl aminoacetate betaine, and the like can be mentioned.The amount of these surfactants used is not particularly limited. For example, among the solid content of the emulsion, 1 to 20% by mass is preferable, and more preferably 1.5 to 10% by mass.

[0204] The hydrophilic-lipophilic balance (HLB) of the above emulsifier is not particularly limited. In the non-fluorinated water-repellent agent composition according to one embodiment, the average HLB of the nonionic emulsifier is preferably 6.0 to 16.0, 6.5 to 15.5, 7.0 to 15.0, or 7.5 to 14.5. When the HLB is outside this range, the initial Bundesmann water repellency and the Bundesmann water repellency after wear tend to decrease. Note that the HLB of the emulsifier is the value calculated by the Griffin method, considering the ethyleneoxy group in the emulsifier as the hydrophilic group.

[0205] (Other additives) The water-repellent treatment agent may contain an acid, an alkali, a chelating agent, etc. Further, the water-repellent treatment agent may or may not contain the above isocyanate compound and other crosslinking agents.

[0206] 2.1.3 Content of non-fluorinated water-repellent component The content of the non-fluorinated water-repellent component in the water-repellent treatment agent is not particularly limited. For example, the ratio (mass ratio) of the non-fluorinated water-repellent component in the whole water-repellent treatment agent may be 0.1 to 70% by mass, or 0.5 to 50% by mass.

[0207] 2.2 Contact method In the method for manufacturing a fiber product according to an embodiment, by bringing the above-described non-fluorine-based water-repellent component (a water-repellent treatment agent containing a non-fluorine-based water-repellent component) into contact with the fiber material after the above-described pretreatment, the non-fluorine-based water-repellent component can be adhered to the fiber material. The method of bringing the above-described non-fluorine-based water-repellent component (a water-repellent treatment agent containing a non-fluorine-based water-repellent component) into contact with the above-described fiber material is not particularly limited. For example, processing methods such as an immersion method, a spraying method, and a coating method can be mentioned. The immersion method may be a continuous method or a batch method. In the continuous method, first, the non-fluorine-based water-repellent component is diluted in an aqueous solvent to prepare a water-repellent treatment agent (treatment liquid). Next, the object to be treated (fiber material) is continuously fed into an impregnation device filled with the treatment liquid, the object to be treated is impregnated with the treatment liquid, and then unnecessary treatment liquid is removed. The impregnation device is not particularly limited, and a padder, a kiss roll type application device, a gravure coater type application device, a spray type application device, a foam type application device, a coating type application device, etc. can be preferably adopted, and a padder type is particularly preferable. Subsequently, an operation of removing the solvent remaining on the object to be treated using a dryer is performed. The dryer is not particularly limited, and a spreading dryer such as a hot flue or a tenter is preferable. The continuous method is preferably adopted when the object to be treated is in the form of a fabric such as a woven fabric. On the other hand, the batch method includes, for example, a step of immersing the object to be treated in the treatment liquid and a step of removing the solvent remaining on the treated object. The batch method is preferably adopted when the object to be treated is not in the form of a fabric, for example, in the case of loose wool, top, sliver, roving, tow, yarn, etc., or when it is not suitable for the continuous method such as a knitted fabric. In the immersion step, for example, a vat dyeing machine, a cheese dyeing machine, a jet dyeing machine, an industrial washing machine, a beam dyeing machine, etc. can be used. In the operation of removing the solvent, a hot air dryer such as a cheese dryer, a beam dryer, a tumble dryer, a high-frequency dryer, etc. can be used.

[0208] 2.3 Heat treatment After imparting a water-repellent component to the fiber material, it is preferably heat-treated as appropriate. The temperature conditions are not particularly limited, but mild conditions of 100 to 130 °C can sufficiently develop good water repellency in the fiber product. The temperature conditions may be high-temperature treatment at 130 °C or higher (preferably up to 200 °C), but in such a case, the treatment time can be shortened compared to the case of using a fluorine-based water repellent. Therefore, according to the method for manufacturing a fiber product of the present disclosure, deterioration of the fiber product due to heat can be suppressed, the texture of the fiber product during the water-repellent treatment becomes soft, and sufficient water repellency can be imparted to the fiber product under mild heat treatment conditions, that is, low-temperature curing conditions.

[0209] 2.4 Adhesion amount A non-fluorine-based water-repellent component adheres to the fiber material after the water-repellent treatment. The treatment with the water-repellent treatment agent is preferably carried out in an amount such that the adhesion amount of the non-fluorine-based water-repellent component is 0.1 to 10 parts by mass, or 0.5 to 5 parts by mass, based on 100 parts by mass of the fiber material. Within this range, durable water repellency and texture can be achieved at a high level.

[0210] 3. Combined use of crosslinking agent In the method for manufacturing a fiber product according to an embodiment, particularly when it is desired to improve durable water repellency, in addition to performing the pretreatment and water-repellent treatment on the above-described fiber material, it is preferable to include attaching a crosslinking agent containing methylol melamine, a compound having two or more isocyanate groups or blocked isocyanate groups to the fiber material and heating it. Further, when it is desired to further improve durable water repellency, it is preferable that the pretreatment agent or water-repellent treatment agent contains a non-fluorine-based polymer copolymerized with a monomer having a functional group capable of reacting with the above-described crosslinking agent. The compound having two or more isocyanate groups is as described above. The crosslinking agent may be used alone or in combination of multiple types.

[0211] The crosslinking agent can be attached to the object to be treated (textile product) by, for example, dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing it in water, immersing the object to be treated in the treatment liquid, and drying the treatment liquid adhering to the object to be treated. Then, by heating the crosslinking agent attached to the object to be treated, the reaction among the crosslinking agent, the object to be treated, and the non-fluorine-based water-repellent component can be advanced. In order to sufficiently advance the reaction of the crosslinking agent and more effectively improve the durable water repellency, the heating at this time is preferably carried out at 110 to 180 °C for 1 to 5 minutes. The steps of attaching and heating the crosslinking agent may be carried out simultaneously with the step of treating with the above water-repellent treatment agent. When carried out simultaneously, for example, a second treatment liquid containing a non-fluorine-based water-repellent component and a crosslinking agent is attached to the object to be treated, and after removing water, the crosslinking agent adhering to the object to be treated is further heated. Considering the simplification of the water-repellent processing step, the reduction of heat quantity, and the economy, it is preferable to carry out simultaneously with the treatment step using the second treatment liquid.

[0212] In addition, if the crosslinking agent is used excessively, there is a risk of deteriorating the texture. The above crosslinking agent is preferably used in an amount of 0.01 to 50 parts by mass, or 0.1 to 10 parts by mass, based on 100 parts by mass of the object to be treated (textile product).

[0213] 4. Use The textile product produced through the above pretreatment and water-repellent treatment has excellent water repellency (initial water repellency, durable water repellency, Bundesmann water repellency, and water repellency in natural fibers). In addition, since the textile product does not use fluorine-based compounds, it can be said to be environmentally friendly. Since the textile product has excellent water repellency, it is suitably used for various applications such as lining for down, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, lining for futons, futon drying covers, curtains, or tents, etc., including clothing applications and non-clothing applications.

Examples

[0214] As described above, although one embodiment of the technology of the present disclosure has been described, the technology of the present disclosure can be variously modified other than the above embodiment without departing from the gist thereof. Hereinafter, while showing examples, the technology of the present disclosure will be described in more detail, but the technology of the present disclosure is not limited to the following examples.

[0215] 1. Preparation of pretreatment agent As the pretreatment agent, a treatment liquid containing the following isocyanate compound was prepared.

[0216] (Preparation Example A-1: HDI trimer) As the polyisocyanate, Duranate TPA-100 (isocyanurate type of hexamethylene diisocyanate, Asahi Kasei, NCO group content: 23.1%, NV: 100%) was prepared.

[0217] (Preparation Example A-2: IPDI trimer) In a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas introduction tube, at room temperature, 150 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, manufactured by Evonik) as the polyisocyanate and propylene glycol diacetate (Dawnol (registered trademark) PGDA, manufactured by Ando Parachem Co., Ltd.) as the solvent were mixed to completely dissolve the polyisocyanate, and a PGDA solution of IPDI trimer was obtained. Next, 4.3 parts by mass of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Inc.) was mixed into the PGDA solution. Here, 12.8 parts by mass of polyoxyethylene tridecyl ether phosphate (Rhodafac (registered trademark) range, manufactured by Rhodia, EO: 7 mol) as an emulsifier was added, and the mixture was mixed while appropriately cooling so that the temperature of the mixture became 50°C or lower, and a solution containing 40% by mass of IPDI trimer was obtained.

[0218] (Preparation Example A-3: IPDI trimer / HDI trimer nurate) In a reactor similar to Preparation Example A-2, at room temperature, 42 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) as a polyisocyanate, 98 parts by mass (NCO equivalent: 0.825 mol) of isocyanurate type of hexamethylene diisocyanate (HDI) (Duranate TPA-100, manufactured by Asahi Kasei, NCO group content: 23.1%, NV: 100%), and propylene glycol diacetate (Davanol (registered trademark) PGDA, manufactured by Ando Parachem Co., Ltd.) as a solvent were mixed to completely dissolve the polyisocyanate, and a PGDA solution of IPDI trimer / HDI trimer was obtained. Next, 4.0 parts by mass of N,N-dimethylcyclohexylamine (manufactured by Kanto Chemical Co., Inc.) was mixed into the solution. Then, 11.9 parts by mass of polyoxyethylene tridecyl ether phosphate (Rhodafac (registered trademark) range, manufactured by Rhodia, EO: 10 mol) as an emulsifier was added, and the mixture was mixed while appropriately cooling so that the temperature of the mixture became 50 °C or lower, and a solution containing 70% by mass of IPDI trimer / HDI trimer nurate was obtained.

[0219] (Preparation Example A-4: IPDI trimer / HDI trimer biuret) In a reactor similar to Preparation Example A-2, at room temperature, 42 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) as a polyisocyanate, 98 parts by mass (NCO equivalent: 0.839 mol) of biuret type of hexamethylene diisocyanate (HDI) (Duranate 24A-100, manufactured by Asahi Kasei, NCO group content: 23.5%, NV: 100%) and propylene glycol diacetate (Davanol (registered trademark) PGDA, manufactured by Ando Parachem Co., Ltd.) as a solvent were mixed to completely dissolve the polyisocyanate, and a PGDA solution of IPDI trimer / HDI trimer was obtained. Next, 4.0 parts by mass of N,N-dimethylcyclohexylamine (manufactured by Kanto Chemical Co., Inc.) was mixed into the solution. Then, 11.9 parts by mass of polyoxyethylene tridecyl ether phosphate (Rhodafac (registered trademark) range, manufactured by Rhodia, EO: 10 mol) as an emulsifier was added, and the mixture was mixed while appropriately cooling so that the temperature of the mixture became 50°C or lower, and a solution containing 70% by mass of IPDI trimer / HDI trimer biuret was obtained.

[0220] (Preparation Example A-5: Self-emulsifying type of DMP-blocked product of IPDI / HDI trimer) Trixene Aqua BI-522 (manufactured by Lanxess, solid content 40%) was diluted with pure water so that the solid content became 20%.

[0221] (Preparation Example A-6: DMP-blocked product of IPDI trimer) In a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanat 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) as a polyisocyanate and 150 parts by mass of diethylene glycol ethyl methyl ether (hereinafter sometimes abbreviated as MEDG) as a solvent were mixed at room temperature, and 59.6 parts by mass (0.62 mol) of dimethylpyrazole (DMP) as a blocking agent was added in several portions so that the temperature of the reaction solution did not exceed 50 ° C., and the mixture was stirred for 1 hour. Thereafter, by measuring the Fourier transform infrared (FT-IR) spectrum, it was confirmed that the peak derived from the NCO group (near 2260 cm-1) disappeared and was blocked. Next, 21 parts by mass of NIKKOL BC-25 (HLB=18.5, manufactured by Nikko Chemicals Co., Ltd.) and pure water were added little by little while mixing to obtain a dispersion containing 20% ​​by mass of DMP blocked IPDI trimer.

[0222] (Comparative Preparation Example: Anionic Compound) A resin dispersion liquid containing an anionic compound (dihydroxydiphenylsulfone / formaldehyde condensate, weight average molecular weight 40,000, Nagase O.G. Color Chemicals Co., Ltd., SZ9904, solid content 33%) and acetic acid (80 mass% aqueous solution): 0.5 mL / L was prepared.

[0223] 2. Preparation of water repellent treatment As a water repellent treatment agent, a treatment liquid containing the following non-fluorine-based water repellent component was prepared.

[0224] 2.1 Preparation of acrylic compound dispersion (Preparation example B-1) In an autoclave, 15.6 parts by mass of stearyl acrylate, 0.4 parts by mass of diacetone acrylamide, 0.8 parts by mass of Noigen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 0.2 parts by mass of stearyl trimethylammonium sulfate, 10 parts by mass of tripropylene glycol, and 68.8 parts by mass of water were added and stirred at 45 ° C to obtain a mixed liquid. The mixed liquid was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.2 parts by mass of azobis (isobutylamidine) dihydrochloride was added to the dispersion, and under a nitrogen atmosphere, 4.0 parts by mass of vinyl chloride was continuously pressed into the autoclave so that the internal pressure of the autoclave was maintained at 0.3 MPa, and radical polymerization was performed at 60 ° C for 6 hours to obtain a dispersion containing 20% ​​by mass of acrylic resin.

[0225] (Preparation Examples B-2 and B-3) According to the amounts of ingredients shown in Table 1 below, a dispersion containing 20% ​​by mass of an acrylic resin was obtained in the same manner as in Preparation Example B-1.

[0226] [Table 1]

[0227] 2.2 Preparation of silicone compound dispersion 2.2.1 Alkyl-modified silicone dispersion (Preparation Example B-4: Octadecyl dimethicone dispersion) SiH:SiCH 3 Methyl hydrogen silicone with a molar ratio of 5:5 (measured by 1H NMR (nuclear magnetic resonance)) and a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene as a hydrosilylation catalyst were placed in a flask so that the platinum concentration in the reactants in the system was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 molar equivalent of 1-octadecene was added dropwise to the mixture in the flask for 1 molar equivalent of the reactive group (Si-H) of the methyl hydrogen silicone. The inside of the kettle was heated to 120°C and an addition reaction was carried out for 6 hours to obtain the product R in the following formula (1). 20 , R 21 and R22 is CH 3 and R 23 is C 18 H 37 and a is 40, b is 40, a:b is 1:1, and R 30 ~R 35 is CH 3 An alkyl-modified silicone was obtained. To confirm the completion of the addition reaction, FT-IR (Fourier transform infrared) spectroscopic analysis of the obtained alkyl-modified silicone was performed to confirm that the absorption spectrum derived from the SiH group of methylhydrogen silicone disappeared.

[0228] [Chemical formula]

[0229] 20 parts by mass of the obtained alkyl-modified silicone, 1.2 parts by mass of SPAN40 (sorbitan-based nonionic surfactant, HLB = 6.7), 1.3 parts by mass of TWEEN40 (sorbitan-based nonionic surfactant, HLB = 15.6), 0.5 part by mass of Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene-branched decyl ether, HLB = 10.5), 0.5 part by mass of Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene-branched decyl ether, HLB = 12.5), 0.5 part by mass of stearyltrimethylammonium sulfate, and 10 parts by mass of dipropylene glycol were mixed while heating. Then, 66.0 parts by mass of water was added little by little to the obtained mixture while mixing to obtain a dispersion containing 20% by mass of octadecyl dimethicone (average HLB of nonionic surfactant = 11.4).

[0230] (Preparation Example B-5: Hexacosyl Dimethicone Dispersion) SiH:SiCH 3Methyl hydrogen silicone with a molar ratio of 4:6 (measured by 1H NMR (nuclear magnetic resonance)) and a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene as a hydrosilylation catalyst were placed in a flask so that the platinum concentration in the reactants in the system was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 molar equivalent of 1-hexacosene was added dropwise to the mixture in the flask for 1 molar equivalent of the reactive group (Si-H) of the methyl hydrogen silicone. The inside of the kettle was heated to 120°C and an addition reaction was carried out for 6 hours to obtain the product R in the above formula (1). 20 , R 21 and R 22 CH 3 and R 23 C 26 H 53 a is 60, b is 90, a:b is 2:3, and R 30 ~R 35 CH 3 The completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to FT-IR (Fourier transform infrared) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methyl hydrogen silicone had disappeared.

[0231] Using the obtained alkyl-modified silicone, a dispersion containing 20 mass % hexacosyldimethicone was obtained in the same manner as in Preparation Example B-4 (average HLB of nonionic surfactants = 9.8).

[0232] (Preparation Example B-6: Dotriacontyl Dimethicone Dispersion) SiH:SiCH 3Methylhydrogen silicone with a molar ratio of 3:7 (measured by 1H NMR (nuclear magnetic resonance)), as a hydrosilylation catalyst, a mixed solution of platinum(IV) chloride in ethylene glycol monobutyl ether and toluene was charged into a flask so that the platinum concentration was 5 ppm with respect to the reactants in the system. The inside of the flask was purged with nitrogen, and 1 molar equivalent of 1-docosatriacontene was charged into the mixture in the flask dropwise with respect to 1 molar equivalent of the reactive group (Si-H) of methylhydrogen silicone. The inside of the kettle was heated to 120 °C and subjected to an addition reaction for 6 hours. In the above formula (1), R 20 and R 21 and R 22 are CH 3 , R 23 is C 32 H 65 , a is 140, b is 60, a:b is 7.3, and R 30 to R 35 are CH 3 to obtain an alkyl-modified silicone. The completion of the addition reaction was confirmed by performing FT-IR (Fourier transform infrared) spectroscopic analysis on the obtained alkyl-modified silicone and confirming that the absorption spectrum derived from the SiH group of methylhydrogen silicone disappeared.

[0233] Using the obtained alkyl-modified silicone, in the same manner as in Preparation Example B-4, a dispersion containing 20% by mass of dotriacontyl dimethicone was obtained (average HLB of nonionic surfactant = 8.1).

[0234] The compositions of Preparation Examples B-4 to B-6 and the average HLB of the nonionic surfactant are summarized in Table 2 below.

[0235]

Table 2

[0236] 2.2.2 Dispersion of silicone resin, dimethyl silicone and amino-modified silicone (Preparation Example B-7) 5.8 parts by mass of MQ-1600 (a trimethylsilyl group-containing polysiloxane, manufactured by Toray Dow Corning Co., Ltd., trade name) as a silicone resin and 13.4 parts by mass of KF-96A-100cs (manufactured by Shin-Etsu Silicone Co., Ltd.) as dimethyl silicone were added to a 300 mL stainless steel pot, and the mixture was heated and stirred until the silicone resin was uniformly dissolved. To the resulting uniform solution, 0.8 part by mass of KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., an amino-modified silicone with amino groups at both ends and a functional group equivalent of 2200) as an amino-modified silicone was added to obtain a mixture. Next, 1.6 parts by mass of Neugen XL-40 was added, and 78.4 parts by mass of water was added little by little while mixing. After ultrasonic treatment at 60 to 70 °C for 10 minutes using an ultrasonic emulsifier, the mixture was cooled to room temperature to obtain a dispersion containing 20% by mass of a silicone-based compound (average HLB of nonionic surfactant = 10.5).

[0237] (Preparation Example B-8) A dispersion containing 20% by mass of a silicone-based compound (average HLB of nonionic surfactant = 4.7) was obtained in the same manner as in Preparation Example B-7, except that the blending ratio shown in Table 3 below was used.

[0238] (Preparation Example B-9) A dispersion containing 20% by mass of a silicone-based compound (average HLB of nonionic surfactant = 18.3) was obtained in the same manner as in Preparation Example B-7, except that the blending ratio shown in Table 3 below was used.

[0239] (Preparation Example B-10) A dispersion containing 20% by mass of a silicone-based compound (average HLB of nonionic surfactant = 10.5) was obtained in the same manner as in Preparation Example B-7, except that the blending ratio shown in Table 3 below was used.

[0240] 2.2.3 Dispersion of Amino-Modified Silicone (Preparation Example B-11) Using WACKER FINISH WR 301 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd., amine equivalent 3700, solid content 100%) as the amino-modified silicone, a dispersion containing 20% by mass of the silicone-based compound was obtained in the same manner as in Preparation Example B-7, except that the mixing ratio shown in Table 3 below was used (average HLB of the nonionic surfactant = 12.0).

[0241] 2.2.4 Dispersion of silicone resin (Preparation Example B-12) Using IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.) as the solvent, a dispersion containing 20% by mass of the silicone resin was obtained in the same manner as in Preparation Example A-7, except that the mixing ratio shown in Table 3 below was used (average HLB of the nonionic surfactant = 4.7).

[0242]

Table 3

[0243] 2.3 Preparation of dispersion of wax-based compound (Preparation Example B-13) 20 parts by mass of Paraffin Wax-155 (manufactured by Nippon Seiro Co., Ltd., melting point 69°C), 78 parts by mass of water, 1.0 part by mass of sorbitan monostearate (HLB = 4.5), and 1.0 part by mass of polyoxyethylene sorbitan monostearate (HLB = 14.9) were placed in a high-pressure reaction vessel and sealed. Then, the temperature inside the vessel was raised to 110 - 120°C while stirring. Thereafter, high-pressure emulsification was carried out for 30 minutes while maintaining high pressure inside the vessel to obtain an emulsion containing 20% by mass of paraffin wax (average HLB of the nonionic surfactant = 9.7).

[0244] 2.4 Preparation of dispersion of urethane-based compound 2.4.1 Synthesis of polyurethane resin (Synthesis Example U-1) In a reactor equipped with a thermometer, a stirring device, a nitrogen inlet tube, and a cooling tube, under a nitrogen atmosphere, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (alias: dibutylhydroxytoluene, BHT, a hindered phenolic antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (an organic phosphite ester, a co-catalyst) were mixed. Then, 10.7 parts by mass of 1,3-butanediol was added to this mixed solution, and nitrogen was introduced into its liquid phase for 1 hour. Thereafter, the mixed solution was heated to 80°C and reacted for 3 hours, and then cooled to 60°C. Thereafter, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanuration catalyst and reacted for 1.5 hours. Thereafter, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. Thereafter, this reaction mixture was passed through a thin-film distillation apparatus (temperature 150°C, degree of vacuum 93.3 Pa) and distilled until the amount of residual HDI monomer became 0.5% or less, to obtain an aliphatic polyisocyanate derivative (an isocyanurate derivative of hexamethylene diisocyanate). The isocyanate group content of the obtained aliphatic polyisocyanate derivative was 20.9%, and the average number of isocyanate functional groups was 3.0.

[0245] 2.4.2 Preparation of a dispersion of a polyurethane resin (Preparation Example B-14) Into a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, 100.08 parts by mass of the aliphatic polyisocyanate derivative of Synthesis Example U-1 as an aliphatic polyisocyanate derivative and 90.03 parts by mass of Calcohol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound were mixed, and the mixture was reacted at 110 °C in a nitrogen atmosphere for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction solution was cooled to 80 °C, 9.89 parts by mass of N-methyldiethanolamine was added as a cationic active hydrogen compound, and the mixture was reacted at 80 °C for 1 hour. 50 parts by mass of methyl ethyl ketone was added as a solvent, and the reaction was carried out at 80 °C until it was confirmed by infrared absorption spectrum that the isocyanate groups had disappeared. Next, 57.7 parts by mass of methyl ethyl ketone (MEK) was added to the reaction solution, the temperature was raised to 80 °C, and the mixture was mixed until the reaction solution was completely dissolved, and then cooled to 75 °C. Thereafter, 18.93 parts by mass of acetic acid was added as an acid compound to neutralize it. Next, while maintaining the reaction solution at 75 °C, 20 parts by mass of NIKKOL Hexaglyn 1-SV (HLB = 9.0, manufactured by Nikko Chemicals Co., Ltd.) was added and mixed, and 800 parts by mass of ion-exchanged water heated to 70 °C was gradually added to emulsify it. Next, MEK was distilled off with an evaporator under reduced pressure at a water bath temperature of 60 °C. Next, a dispersion containing a polyurethane resin was obtained by adjusting with ion-exchanged water so that the solid content concentration became 20% by mass (average HLB of nonionic surfactant = 9.0, solid content 20% by mass).

[0246] 2.5 Preparation of Dispersion of Dendrimer-Based Compound (Preparation Example B-15) To a four-necked round-bottom flask equipped with an overhead stirrer, a thermocouple, and a Dean-Stark / cooling tube, 15.3 parts by mass of sorbitan tristearate (hydroxyl value = 77.2 mgKOH / g) and 24.7 parts by mass of 4-methyl-2-pentanone (MIBK) were added. The solution was refluxed for 1 hour to remove the remaining moisture. After 1 hour, the solution was cooled to 50 °C, 4.0 parts by mass of DESMODUR N-100 was added, and then a catalyst was added. The solution was heated for more than 1 hour until it reached 80 °C to obtain a dendrimer solution.

[0247] 52.7 parts by mass of water, 0.7 parts by mass of ARMEEN DM-18D, 2.0 parts by mass of TERGITOL TMN-10, and 0.6 parts by mass of acetic acid were added to a beaker and stirred to prepare a surfactant solution, which was then heated to 60°C. The dendrimer solution prepared above was cooled to 60°C, and the heated surfactant solution was slowly added thereto to prepare a turbid emulsion. After homogenization at 41.37 MPa (6000 psi), the solvent was removed by distillation under reduced pressure to obtain a dispersion containing 20% of the dendrimer-based compound (average HLB of nonionic surfactant = 14.4, solid content 20% by mass).

[0248] 3. Treatment of Fibers The water-repellent treatment of the treated fabric was carried out and its water repellency was evaluated by each of a one-bath treatment in which the treatment was carried out in one step using a treatment liquid containing an isocyanate compound and a water-repellent component, and a two-bath treatment in which the treatment was carried out in two steps using a treatment liquid containing one of these two components and a treatment liquid containing the other component. As the treated fabric, polyester (PET) woven fabric, nylon (Ny) woven fabric, cotton woven fabric, and a woven fabric composed of 50% / 50% polyester / cotton (T / C) were used.

[0249] 3.1 Two-Bath Treatment (Examples 1 to 22, Comparative Example 1) The isocyanate compound dispersion was diluted with water to prepare a first treatment liquid so as to have the composition (mass%) shown in Table 4 or 5 below, and pretreatment was carried out by immersing the treated fabric in the first treatment liquid. After the pretreatment, it was dried at 130°C for 1 minute to obtain a treated fabric (first treated fabric) treated with the first treatment liquid. Thereafter, the water-repellent component dispersion was diluted with water to prepare a second treatment liquid so as to have the composition shown in Table 4 or 5, and the water-repellent treatment was carried out by immersing the first treated fabric in the second treatment liquid. After the water-repellent treatment, it was dried at 100°C or 170°C for 1 minute to obtain a water-repellent fiber product.

[0250] 3.2 One-Bath Treatment (Comparative Examples 2, 3, 5) An isocyanate compound dispersion and a water-repellent component dispersion were mixed and diluted with water to have the composition (mass %) shown in Table 4 or 5 below, thereby preparing a treatment liquid for the same-bath treatment. The treatment fabric was immersed in the treatment liquid to perform a water-repellent treatment. After the water-repellent treatment, it was dried at 100 °C or 170 °C for 1 minute to obtain a water-repellent fiber product.

[0251] 3.3 Water-repellent treatment only (Comparative Example 4) A water-repellent treatment was performed on the treatment fabric without performing a pretreatment. Specifically, a treatment liquid was prepared by diluting a water-repellent component dispersion with water to have the composition (mass %) shown in Table 4 below. The treatment fabric was immersed in the treatment liquid to perform a water-repellent treatment. After the water-repellent treatment, it was dried at 170 °C for 1 minute to obtain a water-repellent fiber product.

[0252] 4. Evaluation method 4.1 Evaluation of the initial water repellency of the fiber product A test was conducted according to the spray method of JIS L1092 (2009) with the shower water temperature set at 20 °C to evaluate the water repellency of the above fiber product. The results were evaluated visually according to the following grades. When the characteristics were slightly better, a "+" was added to the grade, and when the characteristics were slightly inferior, a "-" was added to the grade. Water repellency: State 5: Those with no wet adhesion on the surface 4: Those showing slight wet adhesion on the surface 3: Those showing partial wetness on the surface 2: Those showing wetness on the surface 1: Those showing wetness on the entire surface 0: Those showing complete wetness on both the front and back sides

[0253] 4.2 Evaluation of the durable water repellency of the fiber product The above fiber product was washed 20 times (L-20) or 100 times (L-100) according to the 103 method of JIS L0217 (1995), and the water repellency after air drying was evaluated according to the same procedure and grades as above.

[0254] 4.3 Evaluation of the water repellency of the fiber product after abrasion 4.3.1 Preparation of the abraded fabric According to JIS L1096:2010 Method E (Martindale method), a test piece made of the above fiber product was attached to the sample holder of a Martindale abrasion tester, a standard friction cloth was attached to the friction table of the abrasion tester, the sample holder was placed on it, a pressing load of 9 kPa was applied, and abrasion was carried out 1000 times to obtain an abrasion cloth for evaluation.

[0255] 4.3.2 Evaluation of initial water repellency and durable water repellency of the abrasion cloth The water repellency of the above abrasion cloth was evaluated by the same procedure and grade as above.

[0256] 4.4 Bundesmann rainfall test For each of the above fiber products before abrasion (before washing), after washing, and after abrasion, the water repellency degree, water absorption amount, and water absorption rate were evaluated after performing a rainfall test according to the method described in JIS L1092:2009 7.3 Rain test (shower test) Method A. The rainfall time was 10 minutes. The water repellency degree was determined by the wet state shown in Figure 1 and graded from 1 to 5. The larger the score, the better it indicates. Those marked with +(-) in the grade indicate that each property is slightly better (worse).

[0257] 5. Evaluation results The evaluation results are shown in Tables 4 and 5 below.

[0258]

Table 4

[0259]

Table 5

[0260] From the results shown in Tables 4 and 5, the following can be understood. (1) When the fiber material is pretreated with an isocyanate compound and then subjected to a water-repellent treatment with a non-fluorine-based water-repellent component in a separate bath treatment (Examples 1 to 21), the washing durable water repellency, Bundesmann rainfall test, and water repellency in natural fibers of the fiber product are improved compared to the case where the water-repellent treatment is performed in a same bath treatment (Comparative Examples 2 and 3). (2) The effect of the above separate bath treatment is more excellent when an unblocked isocyanate is employed (Example 2) than when a blocked isocyanate is employed (Example 6) as the isocyanate compound during the pretreatment. (3) Regarding the case where low-temperature drying is performed after the water-repellent treatment, comparing the separate bath treatment (Example 22) with the same bath treatment (Comparative Example 5), the separate bath treatment can ensure sufficient washing durable water repellent performance.

[0261] From the above results, according to the manufacturing method of a fiber product including contacting a fiber material with an isocyanate compound and contacting the fiber material after contacting with the isocyanate compound with a non-fluorine-based water-repellent component, it can be said that a fiber product having excellent water repellency can be manufactured.

[0262] In addition, in the above examples, a form of imparting water repellency to a fiber product using an isocyanate group-containing compound and a non-fluorine-based water repellent composition was exemplified, but the technology of the present disclosure is not limited to this form. It is considered that the treatment method of the present disclosure can impart excellent initial water repellency and durable water repellency to various articles other than fiber products. In particular, as shown in the above examples, it is suitable for imparting durable water repellency, Bundesmann water repellency, and water repellency in natural fibers to fiber products.

Claims

1. contacting a fiber material with an isocyanate compound, and contacting the fiber material after contacting with the isocyanate compound with a non-fluorine-based water-repellent component, A method for manufacturing a fiber product, comprising:

2. The method for manufacturing a fiber product according to claim 1, wherein the isocyanate compound is a polyisocyanate.

3. The method for manufacturing a fiber product according to claim 1, wherein the isocyanate compound is at least one of an aliphatic isocyanate, an aromatic isocyanate, an aromatic aliphatic isocyanate, and an alicyclic isocyanate.

4. The method for manufacturing a fiber product according to any one of claims 1 to 3, wherein the isocyanate compound is an unblocked isocyanate.

5. The method for manufacturing a fiber product according to any one of claims 1 to 3, wherein the non-fluorine-based water-repellent component is at least one of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound.

6. The method for manufacturing a fiber product according to any one of claims 1 to 3, wherein the non-fluorine-based water-repellent component is at least one of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound. ​ ​

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